CN117186610A - Polylactic acid and polybutylene succinate composite material for straw and preparation method thereof - Google Patents
Polylactic acid and polybutylene succinate composite material for straw and preparation method thereof Download PDFInfo
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- CN117186610A CN117186610A CN202311262241.9A CN202311262241A CN117186610A CN 117186610 A CN117186610 A CN 117186610A CN 202311262241 A CN202311262241 A CN 202311262241A CN 117186610 A CN117186610 A CN 117186610A
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- 229920002961 polybutylene succinate Polymers 0.000 title claims abstract description 77
- 239000004631 polybutylene succinate Substances 0.000 title claims abstract description 77
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 63
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 62
- -1 polybutylene succinate Polymers 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010902 straw Substances 0.000 title claims description 13
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000011258 core-shell material Substances 0.000 claims abstract description 37
- 229920001634 Copolyester Polymers 0.000 claims abstract description 36
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000001384 succinic acid Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000000137 annealing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005303 weighing Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- 229960005137 succinic acid Drugs 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical group C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- JCHMFMSWRWHRFI-HMMYKYKNSA-N ethyl (2e)-2-[(2,5-dichlorophenyl)hydrazinylidene]-2-(2,6-dimethylmorpholin-4-yl)acetate Chemical group C1C(C)OC(C)CN1/C(C(=O)OCC)=N/NC1=CC(Cl)=CC=C1Cl JCHMFMSWRWHRFI-HMMYKYKNSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a polylactic acid and polybutylene succinate composite material for a suction pipe and a preparation method thereof, belonging to the field of environment-friendly biodegradable materials; the polylactic acid and polybutylene succinate composite material for the suction pipe comprises the following raw materials in parts by weight: 30-75 parts of polylactic acid, 10-40 parts of polybutylene succinate, 5-10 parts of PBS-CO-PLLA copolyester with a core-shell structure and 10-20 parts of inorganic minerals; the prepared polylactic acid and polybutylene succinate material for the suction pipe has high toughness, excellent heat resistance, heat deformation temperature of 98 ℃ after annealing treatment, no pungent smell, controllable melt finger and easy processing, and can improve pain points in the use process of the current suction pipe material.
Description
Technical Field
The invention belongs to the field of environment-friendly biodegradable materials, and particularly relates to a polylactic acid and polybutylene succinate composite material for a suction pipe and a preparation method thereof.
Background
Polylactic acid (PLA) takes lactic acid fermented by corn starch, tapioca starch, straw and the like as a raw material, and is obtained by lactide ring-opening polymerization, and is derived from renewable resources and can be biodegraded into substances harmless to the environment such as water, carbon dioxide and the like. Polylactic acid has the characteristics of high strength and modulus, easy processing, safety, no degree and the like, and can be used in the fields of disposable tableware, hotel articles, packaging materials and the like, but the polylactic acid material has poor toughness and low heat-resistant temperature, so that the application range of the polylactic acid material is severely limited.
The monomer of the polybutylene succinate (PBS) mainly comes from petrochemical industry, but has good toughness, heat resistance, crystallinity and degradability.
Polybutylene succinate is often added into polylactic acid to improve toughness, heat resistance and processability of the material, but PBS and PLA belong to a thermodynamically incompatible blending system, and the interfacial force is weak and phase separation is easy to occur. When the PBS content is small, the PBS can be dispersed in a rigid PLA matrix as rubber particles, and the PBS can exert toughening effect by consuming external force through the functions of deformation, debonding with the matrix, shearing yielding and the like, but the size of PBS colloidal particles becomes large along with the increase of the PBS content, the phase separation phenomenon becomes strong, the external force can not be effectively transferred from the PLA matrix to the PBS colloidal particles, the toughening effect is reduced, and the toughening effect of the PBS on the PLA can be effectively improved by improving the compatibility of the PLA and the PBS.
Aiming at the technical problem of toughening PLA by PBS, the prior main improvement mainly comprises adding a chain extender and a catalyst, and reacting with PLA and the end group of the PBS by reactive extrusion, wherein the technical proposal can improve the compatibility of the PBS and the PLA to a certain extent, but the performance of the composite material has certain defects.
For example, chinese patents CN113354929A, CN108948694A, CN114213824A, CN 114752198A, CN116162339a, etc., react with the end groups of PLA and PBS by using a polyepoxide compound, a prepolymer containing a polyepoxy group, a dianhydride, a compound containing a polyacid anhydride group, an isocyanate compound, a polyisocyanate prepolymer, pyromellitic dianhydride, triglycidyl isocyanurate, a chain extender such as dicumyl peroxide, etc., or a catalyst such as tin monobutyl triisooctoate, tin dibutyl dilaurate, etc., to improve the compatibility of PBS and PLA, and improve the performance of the composite material. However, the reactive extrusion process has short time, the reaction degree is difficult to control, the fluidity is easy to reduce, and the pungent odor is easy to generate along with side reaction.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polylactic acid and polybutylene succinate composite material for a suction pipe and a preparation method thereof, and solves the problems in the prior art.
The aim of the invention can be achieved by the following technical scheme:
the polylactic acid and polybutylene succinate composite material for the suction pipe comprises the following raw materials in parts by weight: 30-75 parts of polylactic acid, 10-40 parts of polybutylene succinate, 5-10 parts of PBS-CO-PLLA copolyester with a core-shell structure and 10-20 parts of inorganic minerals.
Further, the PBS-CO-PLLA copolyester with a core-shell structure has the structural formula:
further, the inorganic mineral is at least one of silica, talc and calcium carbonate, and has a particle diameter of 5 to 10 μm.
A preparation method of polylactic acid and polybutylene succinate composite material for a suction pipe comprises the following steps:
step 1: according to the mass parts, sequentially adding 30-75 parts of polylactic acid, 10-40 parts of polybutylene succinate, 5-10 parts of PBS-CO-PLLA copolyester with a core-shell structure and 10-20 parts of inorganic mineral into a high-speed mixer for mixing for 3min at 500-800 r/min;
step 2: and (3) putting the mixed material into a parallel double-screw extruder, and performing melt extrusion granulation to obtain the polylactic acid and polybutylene succinate composite material for the suction pipe.
Further, the main machine rotation speed of the parallel double-screw extruder is 200-300rpm, and the temperatures of all the zones are set as follows: 150-170 ℃ in the first area, 170-190 ℃ in the second area, 175-195 ℃ in the third area, 175-195 ℃ in the fourth area, 175-195 ℃ in the fifth area, 175-195 ℃ in the sixth area, 175-195 ℃ in the seventh area, 170-190 ℃ in the eighth area, 170-190 ℃ in the tenth area, 170-190 ℃ in the eleventh area, 170-190 ℃ in the twelve area, 180-200 ℃ in the thirteenth area, 180-200 ℃ in the fourteenth area, wherein the eighth and tenth sections of screw barrels are vacuumized, the vacuum degree is 0.08MPa, and the extruded material strips are subjected to water cooling and grain cutting and then are baked until the water content is lower than 500ppm.
PBS-CO-PLLA copolyester with core-shell structure has the structural formula:
the preparation method of the PBS-CO-PLLA copolyester with the core-shell structure comprises the following steps of:
s1, sequentially adding absolute ethyl alcohol, tetraethyl orthosilicate and deionized water into a container, stirring to obtain a mixed solution, dropwise adding the mixture of ammonia water and absolute ethyl alcohol into the mixed solution, stirring, suction filtering and drying to obtain monodisperse nano particles;
s2, dispersing the monodisperse nano particles in a 1, 4-succinic acid solution under the condition of stirring in a nitrogen atmosphere, reacting in an oil bath at 140-150 ℃, adding 1, 4-butanediol and tetra-n-butyl titanate, and esterifying under normal pressure; then decompressing to 0.1MPa, heating to 200-210 ℃, adding tetra-n-butyl titanate for reaction to obtain PBS polymer of 1, 4-butanediol and 1, 4-succinic acid prepolymer coated monodisperse nano particles;
s3, the L-lactide, the PBS prepolymer and the stannous octoate are put into a reaction vessel according to the proportion, nitrogen is introduced into the reaction vessel for protection, the oil bath is heated to 130 ℃ for prepolymerization, and then the temperature is increased to 150-160 ℃ for reaction, so as to obtain the PBS-CO-PLLA coated nanoparticle core-shell polymer.
Further, in S2, the molar ratio of 1, 4-butanediol, 1, 4-succinic acid and tetra-n-butyl titanate is 1.1:1:0.05 to 0.1.
Further, in S3, the mass ratio of L-lactide, PBS prepolymer, and stannous octoate is 1:1 to 6:0.05.
the application of PBS-CO-PLLA copolyester with a core-shell structure as a compatilizer in the preparation of straw composite materials.
The invention has the beneficial effects that:
1. the PBS-CO-PLLA copolyester with a core-shell structure can be used as a non-reactive compatilizer and a nucleating agent of a PBS-PLA composite material; on one hand, the mass ratio of the PBS chain segment to the PLLA chain segment can be controlled through the feeding and reaction time in the two-step polymerization process to form the copolyester with the core-shell structure and different particle diameters; on the other hand, compared with the prior art that the compatibility of the material is improved through the chain extender and the catalyst, the copolyester compatilizer has the following excellent effects that the copolyester PBS and the PLLA chain segments can be respectively compatible with the corresponding base materials of the PBS/PLA composite material to form an entangled structure, so that the interfacial strength and the compatibility of the material are improved, the process is that the physical compatibility is free from chemical reaction, no by-product is generated, and no pungent smell is generated; the molecular weight of the material cannot be increased, so that the melt index is reduced, and the processability of the material is affected; in addition, monodisperse nano particles in the copolyester are connected with a plurality of polylactic acid molecular chains to induce heterogeneous nucleation, so that the crystallization speed is increased.
2. The polylactic acid/polybutylene succinate material for the suction pipe, which is prepared by the invention, has high toughness, excellent heat resistance, heat deformation temperature of 98 ℃ after annealing treatment, no pungent smell, controllable melt finger and easy processing, and can improve pain points in the use process of the current suction pipe material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort.
FIG. 1 shows the structural formula of a core-shell PBS-CO-PLLA copolyester;
FIG. 2 shows the synthetic route of the core-shell structured PBS-CO-PLLA copolyester.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Polylactic acid and polybutylene succinate composite material for the suction pipe is synthesized by taking polylactic acid, polybutylene succinate, inorganic mineral and PBS-CO-PLLA copolyester with a core-shell structure as raw materials; the structural formula of the PBS-CO-PLLA copolyester with the core-shell structure is shown in figure 1;
the following examples are specifically set forth, and it should be noted that the preparation processes in the following examples are all conventional means in the art unless otherwise specified, and therefore are not described in detail; parts in the following embodiments refer to parts by mass;
example 1
As shown in fig. 2, the preparation process of the PBS-CO-PLLA copolyester with a core-shell structure comprises the following steps:
(1) Preparation of monodisperse nanoparticles: sequentially adding 80mL of absolute ethyl alcohol, 20mL of tetraethyl orthosilicate and 10mL of deionized water into a reaction vessel, and magnetically stirring to obtain a mixed solution; and mixing 10mL of ammonia water with 10mL of absolute ethyl alcohol, slowly dripping the mixture into the mixture, magnetically stirring the mixture at normal temperature for reaction for 24 hours, and carrying out suction filtration and drying to obtain the monodisperse nano silicon dioxide particles.
(2) Dispersing the completely dried monodisperse nano particles in a 1, 4-succinic acid solution under the condition of mechanical stirring in a nitrogen atmosphere, reacting for 2 hours at 140 ℃ under the condition of oil bath, and adding 1, 4-butanediol and a catalyst tetra-n-butyl titanate, wherein the 1, 4-butanediol: 1, 4-butanedioic acid: the molar ratio of the catalyst is 1.1:1:0.05, carrying out esterification reaction for 4 hours under normal pressure; then decompressing to 0.1MPa, heating to 200 ℃, adding a catalyst tetra-n-butyl titanate with the 1, 4-butanediol molar ratio of 0.05% to react for 8 hours to obtain a PBS polymer of 1, 4-butanediol, wherein the PBS polymer is formed by coating monodisperse nano particles with a 1, 4-succinic acid prepolymer;
(3) Mixing L-lactide, PBS prepolymer and stannous octoate according to a mass ratio of 1:1:0.05 is put into a reaction vessel, the vessel is quickly closed, nitrogen is introduced for protection, the oil bath is heated to 130 ℃ for prepolymerization for 1h, and then the temperature is increased to 150 ℃ for reaction for 3h, so as to obtain the PBS-CO-PLLA coated nanoparticle core-shell polymer; the prepared core-shell crystallization copolyester is mainly based on PBS shell.
Example 2
The preparation process of the PBS-CO-PLLA copolyester with the core-shell structure comprises the following steps:
(1) Preparation of monodisperse nanoparticles: sequentially adding 80mL of absolute ethyl alcohol, 20mL of tetraethyl orthosilicate and 10mL of deionized water into a reaction vessel, magnetically stirring, slowly dripping the mixture of 10mL of ammonia water and 10mL of absolute ethyl alcohol into the mixed solution, magnetically stirring at normal temperature, reacting for 24h, filtering, and drying to obtain monodisperse nano silicon dioxide particles.
(2) Dispersing the completely dried monodisperse nano particles in a 1, 4-succinic acid solution under the condition of mechanical stirring in a nitrogen atmosphere, reacting for 2 hours at 150 ℃ under the condition of oil bath, and adding 1, 4-butanediol and a catalyst tetra-n-butyl titanate, preferably 1, 4-butanediol: 1, 4-butanedioic acid: the molar ratio of the catalyst is 1.1:1:0.1, carrying out esterification reaction for 4 hours under normal pressure; then decompressing to 0.1MPa, heating to 210 ℃, adding a catalyst tetra-n-butyl titanate with the 1, 4-butanediol molar ratio of 0.1% to react for 3 hours to obtain a PBS polymer of 1, 4-butanediol, wherein the PBS polymer is formed by coating monodisperse nano particles with a 1, 4-succinic acid prepolymer;
(3) Mixing L-lactide, PBS prepolymer and stannous octoate according to a mass ratio of 1:6: and (3) putting 0.05 into a reaction container, quickly sealing the container, introducing nitrogen for protection, heating to 130 ℃ in an oil bath for prepolymerization for 1h, and then heating to 160 ℃ for reaction for 8h to obtain the core-shell polymer of the PBS-CO-PLA coated nano particles, wherein the prepared core-shell crystalline copolyester is mainly PLLA shells.
Example 3
Weighing the following raw materials in parts by weight: 30 parts of polylactic acid, 40 parts of polybutylene succinate, 10 parts of PBS-CO-PLLA copolyester with a core-shell structure prepared in example 2 and 20 parts of talcum powder with a particle size of 5 mu m;
the process for preparing the polylactic acid and polybutylene succinate material for the suction pipe by using the raw materials comprises the following steps:
the raw materials are sequentially put into a high-speed mixer for mixing for 3min at 800r/min, the mixed materials are put into a parallel double-screw extruder, the rotation speed of a main machine of the parallel double-screw extruder is 300rpm, and the temperatures of all the areas are set as follows: 150-170 ℃ in the first area, 170-190 ℃ in the second area, 175-195 ℃ in the third area, 175-195 ℃ in the fourth area, 175-195 ℃ in the fifth area, 175-195 ℃ in the sixth area, 175-195 ℃ in the seventh area, 170-190 ℃ in the eighth area, 170-190 ℃ in the tenth area, 170-190 ℃ in the eleventh area, 170-190 ℃ in the twelve area, 180-200 ℃ in the thirteenth area, 180-200 ℃ in the fourteenth area, wherein the eighth and tenth sections of screw barrels are vacuumized, the vacuum degree is 0.08MPa, and the extruded material strips are subjected to water cooling and grain cutting and then are baked until the water content is lower than 500ppm.
Example 4
Weighing the following raw materials in parts by weight: 38 parts of polylactic acid, 40 parts of polybutylene succinate, 7 parts of PBS-CO-PLLA copolyester with a core-shell structure prepared in example 2 and 15 parts of talcum powder with a particle size of 5 mu m;
the process for preparing the polylactic acid and polybutylene succinate material for the suction pipe by using the raw materials comprises the following steps:
the raw materials are sequentially put into a high-speed mixer for 650r/min mixing for 3min, the mixed materials are put into a parallel double-screw extruder, the rotation speed of a main machine of the parallel double-screw extruder is 250rpm, and the temperatures of all the areas are set as follows: 150-170 ℃ in the first area, 170-190 ℃ in the second area, 175-195 ℃ in the third area, 175-195 ℃ in the fourth area, 175-195 ℃ in the fifth area, 175-195 ℃ in the sixth area, 175-195 ℃ in the seventh area, 170-190 ℃ in the eighth area, 170-190 ℃ in the tenth area, 170-190 ℃ in the eleventh area, 170-190 ℃ in the twelve area, 180-200 ℃ in the thirteenth area, 180-200 ℃ in the fourteenth area, wherein the eighth and tenth sections of screw barrels are vacuumized, the vacuum degree is 0.08MPa, and the extruded material strips are subjected to water cooling and grain cutting and then are baked until the water content is lower than 500ppm.
Example 5
Weighing the following raw materials in parts by weight: 45 parts of polylactic acid, 40 parts of polybutylene succinate, 5 parts of PBS-CO-PLLA copolyester with a core-shell structure prepared in example 2 and 10 parts of talcum powder with a particle size of 5 mu m;
the process for preparing the polylactic acid and polybutylene succinate material for the suction pipe by using the raw materials comprises the following steps:
the raw materials are sequentially put into a high-speed mixer for 500r/min and mixed for 3min, the mixed materials are put into a parallel double-screw extruder, the rotation speed of a main machine of the parallel double-screw extruder is 200rpm, and the temperatures of all the areas are set as follows: 150-170 ℃ in the first area, 170-190 ℃ in the second area, 175-195 ℃ in the third area, 175-195 ℃ in the fourth area, 175-195 ℃ in the fifth area, 175-195 ℃ in the sixth area, 175-195 ℃ in the seventh area, 170-190 ℃ in the eighth area, 170-190 ℃ in the tenth area, 170-190 ℃ in the eleventh area, 170-190 ℃ in the twelve area, 180-200 ℃ in the thirteenth area, 180-200 ℃ in the fourteenth area, wherein the eighth and tenth sections of screw barrels are vacuumized, the vacuum degree is 0.08MPa, and the extruded material strips are subjected to water cooling and grain cutting and then are baked until the water content is lower than 500ppm.
Example 6
Weighing the following raw materials in parts by weight: 55 parts of polylactic acid, 15 parts of polybutylene succinate, 10 parts of PBS-CO-PLLA copolyester with a core-shell structure prepared in example 1 and 20 parts of talcum powder with the particle size of 10 mu m;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 3 and using the above raw materials.
Example 7
Weighing the following raw materials in parts by weight: 62 parts of polylactic acid, 15 parts of polybutylene succinate, 8 parts of PBS-CO-PLLA copolyester with a core-shell structure prepared in example 1 and 15 parts of talcum powder with the particle size of 10 mu m;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 4 and using the above-described raw materials.
Example 8
Weighing the following raw materials in parts by weight: 68 parts of polylactic acid, 15 parts of polybutylene succinate, 7 parts of PBS-CO-PLLA copolyester with a core-shell structure prepared in example 1 and 10 parts of talcum powder with the particle size of 10 mu m;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 5 and using the above raw materials.
Example 9
Weighing the following raw materials in parts by weight: 75 parts of polylactic acid, 10 parts of polybutylene succinate, 5 parts of PBS-CO-PLLA copolyester with a core-shell structure prepared in example 1 and 10 parts of silicon dioxide with the particle size of 8 mu m;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 5 and using the above raw materials.
Comparative example 1
Weighing the following raw materials in parts by weight: 40 parts of polylactic acid, 45 parts of polybutylene succinate and 15 parts of talcum powder with the particle size of 10 mu m;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 4 and using the above-described raw materials.
Comparative example 2
Weighing the following raw materials in parts by weight: 40 parts of polylactic acid, 45 parts of polybutylene succinate, 15 parts of talcum powder with the particle size of 10 mu m and 44680.3 parts of basf polyepoxy chain extender ADR;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 4 and using the above-described raw materials.
Comparative example 3
Weighing the following raw materials in parts by weight: 58 parts of polylactic acid, 22 parts of polybutylene succinate, 20 parts of talcum powder with the particle size of 5 mu m and 44680.3 parts of basf polyepoxy chain extender ADR;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 3 and using the above raw materials.
Comparative example 4
Weighing the following raw materials in parts by weight: 70 parts of polylactic acid, 20 parts of polybutylene succinate, 10 parts of silicon dioxide with the particle size of 8 mu m and 0.3 part of methyl diphenyl diisocyanate;
polylactic acid and polybutylene succinate materials for suction pipes were prepared using the same procedure as in example 5 and using the above raw materials.
Experiment verification;
the composite materials obtained in examples 3 to 9 and comparative examples 1 to 4 were injection molded into standard bars, and the notched impact strength and the heat distortion temperature of the cantilever bars were tested, wherein the heat distortion temperature bars of examples 6 to 9 and comparative examples 3 to 4 were annealed at 90℃for 10 minutes and then tested, the notched impact strength test method of the cantilever bars was specified in CB/T1843, and the heat distortion temperature test method was specified in GB/T1634; melt index test method of modified particles is regulated according to GB/T3682; meanwhile, whether the modified particles have pungent odor is evaluated, wherein 50g of the modified particles are put into a 1L odor test bottle to be sealed, the modified particles are taken out after being treated in an oven at 80 ℃ for 2 hours, and the bottle is opened when the temperature of the bottle is reduced to 60 ℃ to evaluate the pungent odor.
Comparative test results for examples 3 to 5 and comparative examples 1 to 2 are shown in table 1 below:
table 1 comparative test results for examples 3 to 5 and comparative examples 1 to 2
The comparative test results of examples 6 to 9 and comparative examples 3 to 4 are shown in Table 2 below:
table 2 comparative test results for examples 6 to 9 and comparative examples 3 to 4
As is clear from Table 1, by comparing examples 3 to 9 with comparative examples 1 to 4, the overall properties of examples 3 to 9 are significantly better than those of comparative examples, and are characterized by higher impact strength, high heat distortion temperature and no pungent odor. The impact strength of PBS and PLA is obviously improved under the effect of PBS-CO-PLLA copolyester with a core-shell structure, and the melt index is moderate, so that the requirement of extrusion molding of a straw can be met, the extrusion temperature of the straw made of the material can be properly reduced, and the requirement of the straw material on toughness can be met; and secondly, the crystallization speed of the material is high, and the heat deformation temperature of the material is high, so that the heat-resistant requirements of two materials of the heat-resistant straw and the crystallization straw can be met by directly extruding the material. Comparative example 1 has no chain extender, the impact resistance of the material is low, and the produced straw is easy to generate brittle fracture; comparative examples 2 to 4 used the polyepoxide chain extender ADR-4468 and the diisocyanate chain extender methyl diphenyl diisocyanate, and had lower melt index, higher processing temperature, higher current in the suction pipe machine, and a pungent odor.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The polylactic acid and polybutylene succinate composite material for the suction pipe is characterized by comprising the following raw materials in parts by weight: 30-75 parts of polylactic acid, 10-40 parts of polybutylene succinate, 5-10 parts of PBS-CO-PLLA copolyester with a core-shell structure and 10-20 parts of inorganic minerals.
2. The polylactic acid and polybutylene succinate composite material for a straw according to claim 1, wherein the PBS-CO-PLLA copolyester with a core-shell structure has a structural formula as follows:
3. the polylactic acid and polybutylene succinate composite material for a suction pipe according to claim 1, wherein the inorganic mineral is at least one of silica, talcum powder and calcium carbonate, and has a particle size of 5-10 μm.
4. The preparation method of the polylactic acid and polybutylene succinate composite material for the suction pipe is characterized by comprising the following steps of:
step 1: according to the mass parts, sequentially adding 30-75 parts of polylactic acid, 10-40 parts of polybutylene succinate, 5-10 parts of PBS-CO-PLLA copolyester with a core-shell structure and 10-20 parts of inorganic mineral into a high-speed mixer for mixing for 3min at 500-800 r/min;
step 2: and (3) putting the mixed material into a parallel double-screw extruder, and performing melt extrusion granulation to obtain the polylactic acid and polybutylene succinate composite material for the suction pipe.
5. The method for preparing polylactic acid and polybutylene succinate composite material for straw according to claim 4, wherein the main machine rotation speed of the parallel double screw extruder is 200-300rpm, and the temperatures of the areas are set as follows: 150-170 ℃ in the first area, 170-190 ℃ in the second area, 175-195 ℃ in the third area, 175-195 ℃ in the fourth area, 175-195 ℃ in the fifth area, 175-195 ℃ in the sixth area, 175-195 ℃ in the seventh area, 170-190 ℃ in the eighth area, 170-190 ℃ in the tenth area, 170-190 ℃ in the eleventh area, 170-190 ℃ in the twelve area, 180-200 ℃ in the thirteenth area, 180-200 ℃ in the fourteenth area, wherein the eighth and tenth sections of screw barrels are vacuumized, the vacuum degree is 0.08MPa, and the extruded material strips are subjected to water cooling and grain cutting and then are baked until the water content is lower than 500ppm.
6. The PBS-CO-PLLA copolyester with a core-shell structure is characterized by having the structural formula:
7. the method for preparing the PBS-CO-PLLA copolyester with the core-shell structure as set forth in claim 6, which is characterized by comprising the following steps:
s1, sequentially adding absolute ethyl alcohol, tetraethyl orthosilicate and deionized water into a container, stirring to obtain a mixed solution, dropwise adding the mixture of ammonia water and absolute ethyl alcohol into the mixed solution, stirring, suction filtering and drying to obtain monodisperse nano particles;
s2, dispersing the monodisperse nano particles in a 1, 4-succinic acid solution under the condition of stirring in a nitrogen atmosphere, reacting in an oil bath at 140-150 ℃, adding 1, 4-butanediol and tetra-n-butyl titanate, and esterifying under normal pressure; then decompressing to 0.1MPa, heating to 200-210 ℃, adding tetra-n-butyl titanate for reaction to obtain PBS polymer of 1, 4-butanediol and 1, 4-succinic acid prepolymer coated monodisperse nano particles;
s3, the L-lactide, the PBS prepolymer and the stannous octoate are put into a reaction vessel according to the proportion, nitrogen is introduced into the reaction vessel for protection, the oil bath is heated to 130 ℃ for prepolymerization, and then the temperature is increased to 150-160 ℃ for reaction, so as to obtain the PBS-CO-PLLA coated nanoparticle core-shell polymer.
8. The method for preparing the PBS-CO-PLLA copolyester with a core-shell structure according to claim 7, wherein the molar ratio of 1, 4-butanediol, 1, 4-succinic acid and tetra-n-butyl titanate in S2 is 1.1:1:0.05 to 0.1.
9. The method for preparing the core-shell PBS-CO-PLLA copolyester, according to claim 7, wherein in S3, the mass ratio of the L-lactide to the PBS prepolymer to the stannous octoate is 1:1 to 6:0.05.
10. the application of PBS-CO-PLLA copolyester with a core-shell structure as a compatilizer in the preparation of straw composite materials.
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