CN114276655B - Degradable thermoplastic elastomer and preparation method thereof - Google Patents
Degradable thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN114276655B CN114276655B CN202110863921.0A CN202110863921A CN114276655B CN 114276655 B CN114276655 B CN 114276655B CN 202110863921 A CN202110863921 A CN 202110863921A CN 114276655 B CN114276655 B CN 114276655B
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 25
- 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 80
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 40
- 229920001971 elastomer Polymers 0.000 claims abstract description 20
- 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
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 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 4
- 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 3
- -1 aliphatic ammonium salt Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 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 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000001276 controlling effect Effects 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000004344 phenylpropyl group Chemical group 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 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
- 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
- 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
- 235000013925 ferrous lactate Nutrition 0.000 claims description 2
- 239000004225 ferrous lactate Substances 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
- 229960004658 magnesium lactate Drugs 0.000 claims description 2
- 235000015229 magnesium lactate Nutrition 0.000 claims description 2
- 239000000626 magnesium lactate Substances 0.000 claims description 2
- 150000002989 phenols Chemical class 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
- 229940050168 zinc lactate Drugs 0.000 claims description 2
- 235000000193 zinc lactate Nutrition 0.000 claims description 2
- 239000011576 zinc lactate Substances 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 239000008188 pellet Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 8
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- 239000011258 core-shell material Substances 0.000 description 6
- 229910018557 Si O Inorganic materials 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
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- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
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- 230000008018 melting Effects 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 229920006238 degradable plastic Polymers 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- 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
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 239000011165 3D composite Substances 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 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
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
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- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920002635 polyurethane 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 adipic acid butanediol and terephthalic acid butanediol, 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 degradation property of the elastomer are regulated and controlled by regulating the content of the POSS-g-PBAT/PCL. The degradable thermoplastic elastomer prepared by the invention has high strength, high toughness, good 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
Many articles in hotels and restaurants are non-degradable plastic products, such as toothbrushes, combs, bath caps and the like. Comb and toothbrush handle materials are typically obtained by injection molding using non-degradable Polystyrene (PS) or polypropylene (PP). Toothbrush filament materials are typically obtained by fiber forming and rounding (sharpening) from a non-degradable Polyamide (PA). The existing mass-produced degradable material polylactic acid (PLA) has the problems of high hardness, large brittleness, poor fluidity, poor stretchability and the like, is greatly limited in the continuous melt spinning and fiber forming process of the body of the coarse denier monofilament for the toothbrush filament, and has no research and application report of the degradable filament at present. Simply reducing the spinning speed, and under the lower drawing speed, because PLA molecular chains can not form highly oriented crystals, the strength, toughness and thermal stability of the obtained coarse denier fiber are lower, and the performance requirement of the toothbrush filament can not be met. How to balance the strength, resilience and biocompatibility of toothbrush filaments is critical to achieving a degradable toothbrush filament material.
In the field of biodegradable materials, the copolymer (PBAT) of butanediol adipate and polybutylene terephthalate has excellent toughness, the elongation at break (750%) is higher than that of most degradable plastics, the melting point is 120 ℃, and the processing and the forming are easy. However, the hardness is high, the tensile strength (34+/-2 MPa) is required to be improved, and the problems of poor oxygen and water vapor barrier property, high cost and the like limit the wide application of the material.
In order to further improve the mechanical properties of PBAT, various modification methods have been reported, for example, a permeable network structure is formed in a PBAT and a three-dimensional composite polylactic acid (sc-PLA) composite material prepared by a melt blending method, and the permeable network structure shows higher yield stress and modulus (Zhao Hongwei, RSC Advances,2020,10 (18): 10482-10490). There are also reports of improving the mechanical properties and heat resistance of PBAT by adding inorganic nanoparticles, for example, clay nanoparticles (sepiolite, montmorillonite and fluororectorite) are incorporated into PBAT, the barrier effect of nanoclay can improve the thermal stability of PBAT, sepiolite nanoparticles can act as nucleating agents, promote PBAT crystallization, and the reinforcing effect of nanomaterials can improve the elastic modulus and hardness of PBAT (Fukushima kiku, materials Science and Engineering C,2012, 32 (6): 1331-1351). CaCO is directly extruded by adopting a melt extrusion method 3 Incorporation into PLA/PBAT composites, caCO 3 Although the addition of (3) improves the mechanical properties of the composite, its thermal stability is reduced (Rocha Daniel Belchior, journal of Applied Polymer Science,2018,135 (35): 46660). Nano SiO by utilizing gamma-methacryloxypropyl trimethoxy silane (KH 570) 2 Surface modification is carried out, and modified nano SiO is carried out 2 Filled PLA/PBAT complexesIt was found that as the nano SiO was modified 2 The 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 of the composite system are also improved. But when SiO 2 When excessive, nano SiO is caused 2 The agglomeration and dispersion of the particles are uneven, and the mechanical properties are reduced (Zhou Zhibin, journal of Chemical Engineering of Chinese Universities,2016,30 (6): 1411-1418). This suggests that inorganic nanoparticles have problems of easy agglomeration, uneven dispersion, and poor interfacial compatibility with organic matrices can limit the improvement of PBAT performance. Therefore, the method for improving the performance of the PBAT by only adding other types of polymers or inorganic nano fillers to make up the defects of the PBAT has the limitation, and the key point of improving the performance of the PBAT is to find a method which can play a role in enhancing the effect and improve the stability of the material.
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. Linear polycaprolactone has no high elastic state and no shape memory property, and the cross-linked polycaprolactone has shape memory property, and the larger the cross-linking degree is, the more the winding points are, the larger the elastic modulus is, and the better the shape memory property is. A series of excellent properties enable the polymer to be used in biomedical and textile materials the packaging field shows good application prospect.
Polysilsesquioxane (POSS) is a relatively specific class of siloxane polymers having a chemical composition of (RSiO) 1.5 ) n Between Silica (SiO) 2 ) n With polysiloxanes (R) 2 SiO) n The inorganic core is composed of Si-O alternately connected skeletons, R is an organic group, and the types are varied, and can be any one of amino, carboxyl, hydroxyl, epoxy, epoxycyclohexylethyl, glycidol ether oxypropyl, anhydride, vinyl, acrylic acid group, acryloyloxy, methacryloyloxy and phenylpropyl. The polysilsesquioxane has a high molecular structure which can be annular, cage-shaped or trapezoid-shaped.
The planar annular polysilsesquioxane is organic and inorganic hybridized cyclotetrasiloxane, can be used for enhancing the adhesive force, scratch resistance, temperature resistance and damage resistance of a coating by an epoxy, polyurethane and acrylate system, 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 three-dimensional size of nanometer scale, and belongs to a nanometer compound. The Si-O bond energy is 445.2KJ/mol, and the energy required for destroying the Si-O bond in the POSS inner core is larger. In addition, according to different R group types, grafting or copolymerization reaction can be carried out between the polymer and the polymer, so that chemical bonding action is generated between the polymer and the polymer, uniform dispersion on a molecular level is facilitated, the problems of inorganic particle aggregation and weak two-phase interface binding force are solved, and the performance of the polymer is improved.
The trapezoid 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 bridge groups to form a ladder-like structure. The unique chain structure makes the material have outstanding 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 R groups and the type of coupling agents, so that the hyperbranched degree of the POSS-g-polymer can be 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 condition of POSS, the POSS-g-PBAT/PCL, PBAT and PCL are uniformly mixed, and then the coupling reaction is carried out, so that the degradable thermoplastic elastomer containing a POSS-g-PBAT/PCL core-shell structure or an interpenetrating network structure is finally formed, 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 above purpose, the technical scheme provided by the invention is as follows:
a degradable thermoplastic elastomer having high strength, flexibility, high resilience, heat resistance and biodegradability, the components of which comprise a copolymer of butylene adipate and butylene terephthalate (PBAT), 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 degradation property of the elastomer are regulated and controlled by regulating the content of the POSS-g-PBAT/PCL;
the preparation method of the degradable heat type elastomer comprises the following steps:
1) Preparing POSS-g-PBAT/PCL;
2) Taking a certain amount of POSS-g-PBAT/PCL, PBAT and PCL, and adding into an internal mixer for melt mixing;
3) And adding a coupling agent to crosslink the materials in the subsequent melt mixing process to obtain the degradable thermoplastic elastomer.
The mass fractions of the POSS-g-PBAT/PCL, PBAT, PCL and the coupling agent are respectively 1% -10%, 65% -97%, 1% -30% and 0.1% -2.5%.
Wherein the polysilsesquioxane is ring-shaped, cage-shaped or trapezoid-shaped; the characteristic functional group in the polysiloxane is one or a combination of more of amino, carboxyl, hydroxyl, epoxy, epoxycyclohexylethyl, glycidol ether oxypropyl, anhydride, vinyl, acrylic, acryloyloxy, methacryloyloxy and phenylpropyl.
As a preferred scheme, the polysilsesquioxane is one or a combination of a plurality of glycidyl ether oxypropyl cyclosiloxane, epoxy cyclohexyl ethyl cage polysilsesquioxane, glycidyl ether oxypropyl cage polysilsesquioxane and trapezoid polysilsesquioxane with epoxy cyclohexyl ethyl or glycidyl ether oxypropyl as a side group.
The POSS-g-PBAT/PCL is obtained by reacting a functional group on the 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, phenols, 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 mixing time is 15-30 min.
The coupling agent is selected from one or a combination of a plurality of gamma-aminopropyl triethoxysilane (KH 550), gamma-glycidoxypropyl trimethoxysilane (KH 560), gamma-methacryloxypropyl trimethoxysilane (KH 570), diethylaminomethyl triethylaminosilane, trivinylsilane and vinyltrimethoxysilane.
Compared with the prior art, the invention has the beneficial effects that:
based on the properties, the application and the molecular structure characteristics of PBAT and PCL, the invention adopts Polysilsesquioxane (POSS) with multi-arm epoxy groups to modify the polymer, utilizes the reaction of the epoxy groups in the POSS and the hydroxyl groups in the polymer to form branched polymer, is favorable for the formation of 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 the compatibility of two phases. Meanwhile, the POSS nano compound can be stably present due to the formation of a cross-linked network structure, and the movement range of surrounding molecular chains is limited, so that the mechanical property of the composite material is improved.
According to the invention, the molecular structure is designed according to specific use requirements, and the polysilsesquioxane is connected with the PBAT and the PCL by covalent bonds through the grafting reaction of the reactive groups on the polysilsesquioxane with the PBAT and the PCL. The hyperbranched degree of POSS-g-PBAT/PCL is regulated by regulating the type of polysilsesquioxane, and then the POSS-g-PBAT/PCL, PBAT and PCL are uniformly mixed, 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 content of POSS-g-PBAT/PCL.
The invention can realize the regulation and control of the mechanical property and degradation property of the elastomer by changing the branching degree and crosslinking degree of the molecular chain from the atomic and molecular layers, and is concretely characterized in the following aspects:
firstly, the degradable thermoplastic elastomer prepared by the invention is characterized in that POSS nano-compounds are introduced into a polymer matrix in a covalent bond connection mode by preparing POSS-g-PTAB/PCL with a core-shell structure or a hyperbranched structure, 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 terminate the development of microcrack tips to play a role in reinforcement; in addition, the viscosity of the polymer can be reduced and the flowability of the polymer during processing can be improved by the hyperbranched POSS-g-PTAB/PCL. Secondly, compared with linear polymers, the polymer chain can form a three-dimensional network structure through moderate crosslinking or a certain branching degree, and the movement range of the molecular chain is limited, so that the polymer chain has better toughness and elasticity; in addition, the PCL component after crosslinking also has shape memory property, so that the PCL component has better rebound resilience after being stressed. Third, by introducing Si-O covalent bond with larger bond energy into the elastomer, the heat resistance of the elastomer can be improved. Fourth, the selected materials PBAT and PCL are biodegradable materials, which can endow the elastomer with good degradation performance, and can alleviate the problem of white pollution after the product is used.
Drawings
FIG. 1 molecular structural formula of glycidyl ether oxypropyl cyclotetrasiloxane and its grafted PBAT/PCL.
FIG. 2 molecular structural formula of epoxycyclohexylethyl cage polysilsesquioxane and its grafted PBAT/PCL.
FIG. 3 molecular structural formula of ladder-shaped polysilsesquioxane with glycidyl ether oxypropyl group and its grafted PBAT/PCL.
FIG. 4 side group is a ladder polysilsesquioxane of epoxy cyclohexylethyl and its grafted PBAT/PCL molecular structural formula.
Detailed Description
The above-described matters of the present invention will be further described in detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
The experimental methods used in the examples below are conventional methods, and the reagents, methods and apparatus used are conventional in the art, unless otherwise indicated.
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 mass fraction of the POSS-g-PBAT/PCL is 1% -10%, and specific examples of the preparation of the POSS-g-PBAT/PCL are as follows:
example 1
50 parts of PBAT pellets, 5 parts of PCL pellets and 100 parts of methylene chloride are added into a reaction vessel, and magnetically stirred at room temperature for 6 hours, then 1 part of glycidoxypropyl cyclotetrasiloxane and 0.1 part of ammonium hydroxide are added, and magnetically stirred at room temperature for 3 hours. After the reaction is finished, the dichloromethane solvent is removed by rotary evaporation under the condition of negative pressure, the solvent is washed for 3 times by absolute ethyl alcohol, and the product glycidoxypropyl cyclosiloxane-g-PBAT/PCL is obtained by drying at low temperature (the molecular structural formulas of reactants and products are shown as figure 1).
Example 2
50 parts of PBAT pellets, 5 parts of PCL pellets and 100 parts of methylene chloride are added into a reaction vessel, and magnetically stirred at room temperature for 6 hours, then 1 part of epoxy cyclohexylethyl cage-shaped polysilsesquioxane is added, 0.1 part of ammonium hydroxide is added, and magnetically stirred at room temperature for 4 hours is continued. After the reaction is finished, the dichloromethane solvent is removed by rotary evaporation under the condition of negative pressure, the solvent is washed for 3 times by absolute ethyl alcohol, and the solvent is dried at low temperature, so that the product of epoxy cyclohexyl ethyl cage-shaped polysilsesquioxane-g-PBAT/PCL (the molecular structural formulas of reactants and products are shown as figure 2) is obtained.
Example 3
50 parts of PBAT granules, 5 parts of PCL granules and 100 parts of methylene dichloride are added into a reaction vessel, and magnetically stirred for 6 hours at room temperature, then 1 part of trapezoidal polysilsesquioxane with glycidyl ether oxypropyl groups as side groups is added, 0.1 part of ammonium hydroxide is added, and magnetically stirred for 5 hours at room temperature. After the reaction is finished, the dichloromethane solvent is removed by rotary evaporation under the condition of negative pressure, the solvent is washed for 3 times by absolute ethyl alcohol, and the product of trapezoid polysilsesquioxane-g-PBAT/PCL is obtained by drying at low temperature (the molecular structural formulas of reactants and products are shown as figure 3).
Example 4
50 parts of PBAT granules, 5 parts of PCL granules and 100 parts of methylene dichloride are added into a reaction vessel, and magnetically stirred for 6 hours at room temperature, then 1 part of trapezoid polysilsesquioxane with the side group of cyclohexylethyl epoxide and 0.1 part of ammonium hydroxide are added, and magnetically stirred for 5 hours at room temperature. After the reaction is finished, the dichloromethane solvent is removed by rotary evaporation under the condition of negative pressure, the solvent is washed for 3 times by absolute ethyl alcohol, and the product of trapezoid polysilsesquioxane-g-PBAT/PCL is obtained by drying at low temperature (the molecular structural formulas of reactants and products are shown as figure 4).
Example 5
10 parts of POSS-g-PTAB/PCL, 80 parts of PTAB granules, 10 parts of PCL granules and 570 2 parts of coupling agent KH are added into an internal mixer in sequence, and melt-mixing is carried out at 120 ℃ for 15min. The degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or interpenetrating network structure is prepared.
Example 6
The product obtained in example 2, POSS-g-PTAB/PCL 10 parts, PTAB pellet 80 parts, PCL pellet 10 parts, and coupling agent KH570 2 parts were successively added to an internal mixer, and melt-kneaded at 120℃for 20 minutes. The degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or interpenetrating network structure is prepared.
Example 7
The product obtained in example 3, POSS-g-PTAB/PCL 10 parts, PTAB pellet 80 parts, PCL pellet 10 parts, and coupling agent KH570 2 parts were successively added to an internal mixer, and melt-kneaded at 120℃for 30 minutes. The degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or interpenetrating network structure is prepared.
Example 8
The product obtained in example 4, POSS-g-PTAB/PCL 10 parts, PTAB pellet 80 parts, PCL pellet 10 parts, and coupling agent KH570 2 parts were successively fed into an internal mixer, and melt-kneaded at 120℃for 30 minutes. The degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or interpenetrating network structure is prepared.
Example 9
Preparation of control samples: 80 parts of PTAB granules, 10 parts of PCL granules and 570 2 parts of coupling agent KH were successively added to an internal mixer, and melt-kneading was carried out at 120℃for 15 minutes. A degradable thermoplastic elastomer containing a melt-blended crosslink of PBAT and PCL is prepared.
Example 10
(1) Hardness testing: samples were prepared by a small injection molding machine into square specimens of 30mm by 30 mm. According to GB/T531.1-2008 part 1 of the test method for indentation hardness of vulcanized rubber or thermoplastic rubber: shore durometer (Shore hardness), type A Shore durometer was used for the measurement. Each group of samples was measured 5 times and averaged.
(2) Impact resilience test: samples were prepared by a small injection molding machine into square specimens of 30mm by 2 mm. According to GB/T1681-2009 determination of rubber-vulcanized rubber resilience, measurement was carried out by using a MZ-4065 rubber impact resilience tester. 3 shocks are required before the measurement to correct the mechanical properties of the rubber. Each group of samples was measured 5 times and averaged.
(3) Tensile property detection: determination of Plastic tensile Properties according to detection Standard GB/T1040.3-2006 section 3: test conditions for films and sheets the elastomers obtained in the examples above were prepared into the desired shape for testing tensile strength by means of a small injection molding machine. The total length of the sample 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 25mm. 3 tensile samples were prepared for each group and conditioned for at least 3 hours in an environment having a temperature of (23.+ -. 2) ℃ and a relative humidity of 50%.+ -. 5%. The samples were tested for tensile strength and elongation at break on an electronic tensile tester according to standard ASTM D412-98a test method, with a tensile rate of 5mm/min. Each group of samples was measured 3 times and averaged.
Table 1 test results of hardness, impact resilience, tensile Strength and elongation at break of the test pieces
The present invention is not limited to the preferred embodiments, and any simple modification, equivalent replacement, and improvement made to the above embodiments by those skilled in the art without departing from the technical scope of the present invention, will fall within the scope of the present invention.
Claims (6)
1. A degradable thermoplastic elastomer characterized by: the elastomer has high strength, flexibility, high rebound, heat resistance and biodegradability, and comprises a copolymer (PBAT) of butanediol adipate and butanediol terephthalate, polycaprolactone (PCL), multi-arm polysilsesquioxane grafted PBAT and PCL, namely 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 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 heat type elastomer comprises the following steps:
1) Preparing POSS-g-PBAT/PCL;
2) Taking a certain amount of POSS-g-PBAT/PCL, PBAT and PCL, and adding into an internal mixer for melt mixing;
3) Adding a coupling agent to crosslink the materials in the subsequent melt mixing process to obtain a degradable thermoplastic elastomer;
the mass percentages of the POSS-g-PBAT/PCL, PBAT, PCL and the coupling agent are respectively 1% -10%, 65% -97%, 1% -30% and 0.1% -2.5%;
the POSS-g-PBAT/PCL is obtained by reacting a functional group on the 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, phenols, carboxylic acid, zinc lactate, magnesium lactate and ferrous lactate.
2. The degradable thermoplastic elastomer of claim 1, wherein: wherein the polysilsesquioxane is ring-shaped, cage-shaped or trapezoid-shaped; the characteristic functional group in the polysiloxane is one or a combination of more of amino, carboxyl, hydroxyl, epoxy, anhydride, vinyl and acryloyloxy.
3. The degradable thermoplastic elastomer of claim 2, wherein: the epoxy group is epoxy cyclohexyl ethyl or glycidyl ether oxypropyl, the carboxyl group is acrylic acid group, the acryloyloxy group is methacryloyloxy group, and the amino group is phenylpropyl.
4. The degradable thermoplastic elastomer of claim 2, wherein: the polysilsesquioxane is one or a combination of a plurality of glycidyl ether oxypropyl cyclotetrasiloxane, epoxy cyclohexyl ethyl cage polysilsesquioxane, glycidyl ether oxypropyl cage polysilsesquioxane and trapezoid polysilsesquioxane with epoxy cyclohexyl ethyl or glycidyl ether oxypropyl as a side group.
5. The degradable thermoplastic elastomer of claim 1, wherein: in the step 2), the mixing temperature in an internal mixer is 80-120 ℃ and the mixing time is 15-30 min.
6. The degradable thermoplastic elastomer of claim 1, wherein: the coupling agent is selected from one or a combination of a plurality of gamma-aminopropyl triethoxysilane (KH 550), gamma-glycidoxypropyl trimethoxysilane (KH 560), gamma-methacryloxypropyl trimethoxysilane (KH 570), diethylaminomethyl triethylaminosilane, trivinylsilane and vinyltrimethoxysilane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177193A (en) * | 2008-11-05 | 2011-09-07 | 独立行政法人产业技术综合研究所 | Aliphatic polycarbonate complex derived from carbon dioxide, and process for producing same |
| WO2013164743A1 (en) * | 2012-05-03 | 2013-11-07 | Universita' Di Pisa | Copolymers based on reactive polyesters and plasticisers for the manufacture of transparent, biodegradable packaging film |
| CN110358273A (en) * | 2019-08-13 | 2019-10-22 | 湖南工业大学 | A kind of biomass antibacterial film with high puncturing resistance performance |
| CN110698844A (en) * | 2019-10-28 | 2020-01-17 | 浙江晟祺实业有限公司 | Novel degradable packaging material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177193A (en) * | 2008-11-05 | 2011-09-07 | 独立行政法人产业技术综合研究所 | Aliphatic polycarbonate complex derived from carbon dioxide, and process for producing same |
| WO2013164743A1 (en) * | 2012-05-03 | 2013-11-07 | Universita' Di Pisa | Copolymers based on reactive polyesters and plasticisers for the manufacture of transparent, biodegradable packaging film |
| CN110358273A (en) * | 2019-08-13 | 2019-10-22 | 湖南工业大学 | A kind of biomass antibacterial film with high puncturing resistance performance |
| CN110698844A (en) * | 2019-10-28 | 2020-01-17 | 浙江晟祺实业有限公司 | Novel degradable packaging material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 何宏 ; 龙柱 ; 梁多平 ; 唐义祥 ; .聚己内酯/聚丁二酸丁二醇酯-聚己二酸丁二醇酯共聚物熔融共混体系的力学性能、结晶及流变行为研究.化工新型材料.2013,(第07期),第102-104、109页. * |
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