CN116535836A - A kind of fully biodegradable polylactic acid composite material and its preparation method - Google Patents
A kind of fully biodegradable polylactic acid composite material and its preparation method Download PDFInfo
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 82
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000155 melt Substances 0.000 claims description 16
- 229920002261 Corn starch Polymers 0.000 claims description 11
- 239000008120 corn starch Substances 0.000 claims description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- -1 polybutylene adipate-terephthalate Polymers 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 229920000881 Modified starch Polymers 0.000 claims description 7
- 239000004368 Modified starch Substances 0.000 claims description 7
- 235000019426 modified starch Nutrition 0.000 claims description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 5
- 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 claims description 4
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims 1
- 229920001896 polybutyrate Polymers 0.000 abstract description 17
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 abstract 1
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 229920006348 thermoplastic styrenic block copolymer Polymers 0.000 abstract 1
- 229940099112 cornstarch Drugs 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation 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
- 229920000642 polymer Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WYUHQMAEVAHKNJ-UHFFFAOYSA-N benzene;2-propan-2-ylperoxypropane Chemical compound C1=CC=CC=C1.CC(C)OOC(C)C WYUHQMAEVAHKNJ-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NIGVBLFCGSUSOT-UHFFFAOYSA-N butane-1,4-diol;phthalic acid Chemical compound OCCCCO.OC(=O)C1=CC=CC=C1C(O)=O NIGVBLFCGSUSOT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- 229920001245 poly(D,L-lactide-co-caprolactone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
Description
技术领域technical field
本发明涉及聚乳酸技术领域，尤其涉及一种全生物降解聚乳酸复合材料及制备方法。The invention relates to the technical field of polylactic acid, in particular to a fully biodegradable polylactic acid composite material and a preparation method.
背景技术Background technique
随着环境污染和能源消耗的日益严重，环境友好型高分子材料引起了学术界和工业界的广泛关注。With the increasing environmental pollution and energy consumption, environmentally friendly polymer materials have attracted widespread attention from academia and industry.
聚乳酸(英文简称：PLA；英文全称：Polylactic Acid)，又称聚丙交酯，是以乳酸为主要原料聚合得到的聚酯类聚合物，是一种新型生物降解材料，具有高生物降解性和良好的力学性能。PLA自身的抗冲击性较低，因而限制了其应用。为提高PLA的韧性，现在更经济、更实用的手段是通过将PLA与其他聚合物共混来增韧PLA。其中一种方法是使用不可降解的弹性体来增韧聚乳酸，但这种方法会导致材料降解速率减慢。另一种方法是通过交联剂来改善PLA脆性，然而，改善后的PLA的降解性能较差，且抗冲击性能的改善并不明显。Polylactic acid (English abbreviation: PLA; English full name: Polylactic Acid), also known as polylactide, is a polyester polymer obtained by polymerization of lactic acid as the main raw material. It is a new type of biodegradable material with high biodegradability and Good mechanical properties. The low impact resistance of PLA itself limits its application. In order to improve the toughness of PLA, a more economical and practical means is to toughen PLA by blending PLA with other polymers. One approach is to toughen PLA with non-degradable elastomers, but this approach leads to a slower rate of degradation of the material. Another method is to improve the brittleness of PLA through cross-linking agents. However, the degradation performance of the improved PLA is poor, and the improvement of impact resistance is not obvious.
根据对现有技术检索发现，中国专利CN201510995642公开了一种高韧性聚乳酸复合材料及其制备方法，对弹性体POE、SEBS、ABS进行接枝改性，使用接枝改性后的弹性体增韧聚乳酸来提高复合材料的抗冲击能力。中国专利CN201610680636公开了一种全生物降解PLA/PCL复合材料及其制备方法，选用过氧化苯甲酰和四烃基丙烯酸丁酯作为交联剂，在交联剂的作用下利用PCL增韧PLA。中国专利CN103788605A公开了一种聚乳酸复合材料及其制备方法，其使用TPAS协同PEBA对PLA进行增韧，制备出的PLA复合材料具有高缺口冲击强度。According to the retrieval of the prior art, the Chinese patent CN201510995642 discloses a high-toughness polylactic acid composite material and its preparation method. The elastomers POE, SEBS, and ABS are grafted and modified, and the grafted modified elastomers are used to increase the Tough polylactic acid to improve the impact resistance of composite materials. Chinese patent CN201610680636 discloses a fully biodegradable PLA/PCL composite material and its preparation method. Benzoyl peroxide and butyl acrylate are selected as crosslinking agents, and PCL is used to toughen PLA under the action of crosslinking agents. Chinese patent CN103788605A discloses a polylactic acid composite material and its preparation method, which uses TPAS and PEBA to toughen PLA, and the prepared PLA composite material has high notched impact strength.
发明内容Contents of the invention
本发明提供一种全生物降解聚乳酸复合材料及制备方法，以解决现有聚乳酸材料抗冲击性较低的问题。The invention provides a fully biodegradable polylactic acid composite material and a preparation method to solve the problem of low impact resistance of existing polylactic acid materials.
本发明提供一种全生物降解聚乳酸复合材料的制备方法，该方法包括：The invention provides a method for preparing a fully biodegradable polylactic acid composite material, the method comprising:
S01：将聚己二酸-对苯二甲酸丁二醇酯、甲基丙烯酸缩水甘油酯、N-乙烯基吡咯烷酮和过氧化二异丙苯熔融共混，形成改性聚己二酸-对苯二甲酸丁二醇酯。S01: Melt blend poly(butylene adipate-terephthalate), glycidyl methacrylate, N-vinylpyrrolidone and dicumyl peroxide to form modified poly(adipate-terephthalate) Butylene glycol dicarboxylate.
聚己二酸-对苯二甲酸丁二醇酯(英文全称为Poly(butyleneadipate-co-terephthalate)；英文简称：PBAT)为一种热塑性生物降解塑料，其具有良好的延展性和断裂伸长率、耐热性和抗冲击性，是最受欢迎的生物降解材料之一。本申请中，通过对PBAT接枝改性来提高PBAT与TPS(英文全称为plasticized starch；中文名称：塑化淀粉)、PLA的相容性。具体的，将PBAT、甲基丙烯酸缩水甘油酯(英文全称为Glycidyl methacrylate；英文简称：GMA)、N-乙烯基吡咯烷酮(英文全称为N-vinyl pyrrolidone；英文简称：NVP)和过氧化二异丙苯(英文全称为dicumyl peroxide；英文简称：DCP)按照质量比为100/3/3/0.3放入密炼机或双螺杆挤出机中进行熔融共混，形成改性聚己二酸-对苯二甲酸丁二醇酯。本申请中，将改性聚己二酸-对苯二甲酸丁二醇酯命名为PBAT-g-GMA。其中，熔融共混的温度为180℃，共混时间为5min，转速为80rpm。Poly(butylene adipate-co-terephthalate) (full name in English: Poly(butyleneadipate-co-terephthalate); English abbreviation: PBAT) is a thermoplastic biodegradable plastic with good ductility and elongation at break , heat resistance and impact resistance, it is one of the most popular biodegradable materials. In this application, the compatibility of PBAT with TPS (English full name: plasticized starch; Chinese name: plasticized starch) and PLA is improved by grafting and modifying PBAT. Specifically, PBAT, glycidyl methacrylate (English full name is Glycidyl methacrylate; English abbreviation: GMA), N-vinylpyrrolidone (English full name is N-vinyl pyrrolidone; English abbreviation: NVP) and diisopropyl peroxide Benzene (full name in English is dicumyl peroxide; English abbreviation: DCP) is put into the internal mixer or twin-screw extruder according to the mass ratio of 100/3/3/0.3 for melt blending to form modified polyadipate-para Butylene glycol phthalate. In this application, the modified polybutylene adipate-terephthalate is named as PBAT-g-GMA. Wherein, the temperature of melt blending is 180° C., the blending time is 5 min, and the rotation speed is 80 rpm.
S02：将所述改性聚己二酸-对苯二甲酸丁二醇酯与塑化改性淀粉熔融共混，形成共混物a。S02: melt-blending the modified polybutylene adipate-terephthalate and plasticized modified starch to form a blend a.
本申请中，先使用甘油对玉米淀粉进行改性，以使玉米淀粉具有热塑性。玉米淀粉改性的具体方法包括：将玉米淀粉与甘油按照质量比为3:2混合均匀，静置24h后放入密炼机或双螺杆挤出机中熔融共混，形成塑化改性淀粉，简称为TPS。其中，玉米淀粉与甘油的熔融共混的温度为150℃，共混时间为8min，转速为80rpm。In this application, the cornstarch is firstly modified with glycerol to make the cornstarch thermoplastic. The specific method of corn starch modification includes: mixing corn starch and glycerin according to the mass ratio of 3:2, and putting them into an internal mixer or a twin-screw extruder to melt and blend after standing for 24 hours to form plasticized modified starch , referred to as TPS. Wherein, the melt-blending temperature of cornstarch and glycerin is 150°C, the blending time is 8min, and the rotation speed is 80rpm.
PBAT-g-GMA中的环氧基团与TPS上的羟基发生开环加成反应，由此改善PBAT与TPS之间得相容性，进而为后续形成核壳结构提供了先决条件。具体的，将PBAT-g-GMA与TPS按照质量比为1：1放入密炼机或双螺杆挤出机中熔融共混，形成共混物a。其中，熔融共混的温度为180℃，共混时间为5min，转速为80rpm。The epoxy group in PBAT-g-GMA undergoes a ring-opening addition reaction with the hydroxyl group on TPS, thereby improving the compatibility between PBAT and TPS, which in turn provides a prerequisite for the subsequent formation of a core-shell structure. Specifically, PBAT-g-GMA and TPS are put into an internal mixer or a twin-screw extruder at a mass ratio of 1:1 for melt blending to form a blend a. Wherein, the temperature of melt blending is 180° C., the blending time is 5 min, and the rotation speed is 80 rpm.
S03：将所述改性聚己二酸-对苯二甲酸丁二醇酯与聚乳酸熔融共混，形成共混物b。S03: melt-blending the modified polybutylene adipate-terephthalate and polylactic acid to form a blend b.
PBAT-g-GMA中的环氧基团与PLA上的羧基、羟基发生开环加成反应，进而能够起到增韧PLA的效果。具体的，将PBAT-g-GMA与PLA按照质量比为1：2.3或1:3.68或1:7放入密炼机或双螺杆挤出机中熔融共混，形成共混物b。其中，熔融共混的温度为180℃，共混时间为5min，转速为80rpm。The epoxy group in PBAT-g-GMA undergoes a ring-opening addition reaction with the carboxyl group and hydroxyl group on PLA, which in turn can play a role in toughening PLA. Specifically, PBAT-g-GMA and PLA are melt-blended in an internal mixer or a twin-screw extruder according to a mass ratio of 1:2.3 or 1:3.68 or 1:7 to form a blend b. Wherein, the temperature of melt blending is 180° C., the blending time is 5 min, and the rotation speed is 80 rpm.
S04：所述共混物a和所述共混物b熔融共混，形成全生物降解聚乳酸复合材料。S04: The blend a and the blend b are melt-blended to form a fully biodegradable polylactic acid composite material.
PBAT-g-GMA中的环氧基团分别与TPS上的羟基以及PLA上的羧基、羟基发生开环加成反应，由此，当共混物a和共混物b熔融共混时能够提高三者之间的相容性，进而形成以TPS为核、以PBAT为壳的壳-核结构，进而达到协同增韧的目的。具体的，共混物a与共混物b按照质量比为20:80或11:89放入密炼机或双螺杆挤出机中熔融共混，形成全生物降解聚乳酸复合材料，简称PLA/PBAT-g-GMA/TPS复合材料。其中，熔融共混的温度为180℃，共混时间为5min，转速为80rpm。The epoxy groups in PBAT-g-GMA react with the hydroxyl groups on TPS and the carboxyl groups and hydroxyl groups on PLA respectively, thus, when blend a and blend b are melt blended, it can improve The compatibility between the three forms a shell-core structure with TPS as the core and PBAT as the shell, and then achieves the purpose of synergistic toughening. Specifically, blend a and blend b are melted and blended in an internal mixer or a twin-screw extruder according to a mass ratio of 20:80 or 11:89 to form a fully biodegradable polylactic acid composite material, referred to as PLA/ PBAT-g-GMA/TPS composites. Wherein, the temperature of melt blending is 180° C., the blending time is 5 min, and the rotation speed is 80 rpm.
本发明还提供一种全生物降解聚乳酸复合材料，该复合材料由上述制备方法制备而成，且制备得到的复合材料的缺口冲击强度能够达到93.5kJ/m2。The present invention also provides a fully biodegradable polylactic acid composite material prepared by the above preparation method, and the notched impact strength of the prepared composite material can reach 93.5kJ/m 2 .
本发明的实施例提供的技术方案可以包括以下有益效果：The technical solutions provided by the embodiments of the present invention may include the following beneficial effects:
本发明提供一种全生物降解聚乳酸复合材料及制备方法，该方法中，先对玉米淀粉进行改性，以使改性淀粉具有热塑性。同时，对PBAT进行接枝改性，形成PBAT-g-GMA，以此提高PBAT与TPS、PLA的相容性。将PBAT-g-GMA与TPS和PLA按比例分别进行熔融共混，形成共混物a和共混物b。最后，将共混物a和共混物b按照配比再次进行熔融共混，得到以TPS为核、以PBAT为壳的高韧性、环保的PLA/PBAT-g-GMA/TPS复合材料。本发明采用TPS和PBAT协同增韧PLA，制备出具有高缺口冲击强度的全生物降解聚乳酸复合材料。The invention provides a fully biodegradable polylactic acid composite material and a preparation method. In the method, firstly, corn starch is modified so that the modified starch has thermoplasticity. At the same time, PBAT was grafted and modified to form PBAT-g-GMA, so as to improve the compatibility of PBAT with TPS and PLA. PBAT-g-GMA was melt-blended with TPS and PLA in proportion to form blend a and blend b. Finally, blend a and blend b were melt-blended again according to the ratio to obtain a high-toughness, environmentally friendly PLA/PBAT-g-GMA/TPS composite material with TPS as the core and PBAT as the shell. The invention uses TPS and PBAT to synergistically toughen PLA to prepare a fully biodegradable polylactic acid composite material with high notched impact strength.
应当理解的是，以上的一般描述和后文的细节描述仅是示例性和解释性的，并不能限制本发明。It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.
具体实施方式Detailed ways
下属以具体实施例的形式对本申请实施例提供的全生物降解聚乳酸复合材料的制备方法进行具体描述。The preparation method of the fully biodegradable polylactic acid composite material provided in the examples of the present application is described in detail below in the form of specific examples.
实施例1Example 1
本申请实施例提供一种全生物降解聚乳酸复合材料的制备方法，该方法包括：The embodiment of the present application provides a method for preparing a fully biodegradable polylactic acid composite material, the method comprising:
S101：将PBAT、GMA、NVP和DCP按照质量比为100/3/3/0.3放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PBAT-g-GMA。S101: Put PBAT, GMA, NVP and DCP into an internal mixer or a twin-screw extruder at a mass ratio of 100/3/3/0.3, and melt at a melt blending temperature of 180°C and a rotational speed of 80rpm Blend for 5 min to form PBAT-g-GMA.
S102：将玉米淀粉与甘油按照质量比为3:2混合均匀，静置24h后放入密炼机或双螺杆挤出机中，在熔融共混温度为150℃、转速为80rpm的条件下熔融共混8min，形成TPS。将PBAT-g-GMA与TPS按照质量比为1：1放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成共混物a。S102: Mix cornstarch and glycerin evenly at a mass ratio of 3:2, put them into an internal mixer or a twin-screw extruder after standing for 24 hours, and melt under the conditions of a melt blending temperature of 150°C and a rotation speed of 80rpm Blend for 8 minutes to form TPS. PBAT-g-GMA and TPS were put into an internal mixer or a twin-screw extruder at a mass ratio of 1:1, and melt-blended for 5 minutes at a melt-blending temperature of 180 °C and a rotational speed of 80 rpm to form a blend. mixture a.
S103：将PBAT-g-GMA与PLA按照质量比为1：7放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成共混物b。S103: Put PBAT-g-GMA and PLA into an internal mixer or a twin-screw extruder at a mass ratio of 1:7, and melt blend for 5 minutes at a melt blending temperature of 180°C and a rotational speed of 80 rpm. Blend b is formed.
S104：共混物a与共混物b按照质量比为20:80放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PLA、PBAT-g-GMA、TPS配比为70:20:10的PLA/PBAT-g-GMA/TPS复合材料。S104: Put blend a and blend b into an internal mixer or a twin-screw extruder at a mass ratio of 20:80, and melt blend for 5 minutes at a melt blending temperature of 180°C and a rotational speed of 80 rpm. PLA/PBAT-g-GMA/TPS composites with PLA, PBAT-g-GMA, and TPS ratios of 70:20:10 were formed.
实施例2Example 2
本申请实施例提供一种全生物降解聚乳酸复合材料的制备方法，该方法包括：The embodiment of the present application provides a method for preparing a fully biodegradable polylactic acid composite material, the method comprising:
S201：将PBAT、GMA、NVP和DCP按照质量比为100/3/3/0.3放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PBAT-g-GMA。S201: Put PBAT, GMA, NVP and DCP into an internal mixer or a twin-screw extruder at a mass ratio of 100/3/3/0.3, and melt at a melt blending temperature of 180°C and a rotational speed of 80rpm Blend for 5 min to form PBAT-g-GMA.
S202：将玉米淀粉与甘油按照质量比为3:2混合均匀，静置24h后放入密炼机或双螺杆挤出机中，在熔融共混温度为150℃、转速为80rpm的条件下熔融共混8min，形成TPS。将PBAT-g-GMA与TPS按照质量比为1：1放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成共混物a。S202: Mix cornstarch and glycerin evenly according to the mass ratio of 3:2, put it into an internal mixer or a twin-screw extruder after standing for 24 hours, and melt under the conditions of a melt blending temperature of 150°C and a rotation speed of 80rpm Blend for 8 minutes to form TPS. PBAT-g-GMA and TPS were put into an internal mixer or a twin-screw extruder at a mass ratio of 1:1, and melt-blended for 5 minutes at a melt-blending temperature of 180 °C and a rotational speed of 80 rpm to form a blend. mixture a.
S203：将PBAT-g-GMA与PLA按照质量比为1：3.68放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成共混物b。S203: Put PBAT-g-GMA and PLA into an internal mixer or a twin-screw extruder at a mass ratio of 1:3.68, and melt blend for 5 minutes at a melt blending temperature of 180°C and a rotational speed of 80 rpm, Blend b is formed.
S204：共混物a与共混物b按照质量比为11:89放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PLA、PBAT-g-GMA、TPS配比为70:24.5:5.5的PLA/PBAT-g-GMA/TPS复合材料。S204: Put blend a and blend b into an internal mixer or a twin-screw extruder at a mass ratio of 11:89, and melt blend for 5 minutes at a melt blending temperature of 180°C and a rotational speed of 80 rpm, A PLA/PBAT-g-GMA/TPS composite material with a ratio of PLA, PBAT-g-GMA and TPS of 70:24.5:5.5 was formed.
实施例3Example 3
本申请实施例提供一种全生物降解聚乳酸复合材料的制备方法，该方法包括：The embodiment of the present application provides a method for preparing a fully biodegradable polylactic acid composite material, the method comprising:
S301：将PBAT、GMA、NVP和DCP按照质量比为100/3/3/0.3放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PBAT-g-GMA。S301: Put PBAT, GMA, NVP and DCP into an internal mixer or a twin-screw extruder at a mass ratio of 100/3/3/0.3, and melt at a melt blending temperature of 180°C and a rotational speed of 80rpm Blend for 5 min to form PBAT-g-GMA.
S302：将玉米淀粉与甘油按照质量比为3:2混合均匀，静置24h后放入密炼机或双螺杆挤出机中，在熔融共混温度为150℃、转速为80rpm的条件下熔融共混8min，形成TPS。将PBAT-g-GMA与TPS按照质量比为1：1放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成共混物a。S302: Mix cornstarch and glycerin evenly at a mass ratio of 3:2, put them into an internal mixer or a twin-screw extruder after standing for 24 hours, and melt under the conditions of a melt blending temperature of 150°C and a rotation speed of 80rpm Blend for 8 minutes to form TPS. PBAT-g-GMA and TPS were put into an internal mixer or a twin-screw extruder at a mass ratio of 1:1, and melt-blended for 5 minutes at a melt-blending temperature of 180 °C and a rotational speed of 80 rpm to form a blend. mixture a.
S303：将PBAT-g-GMA与PLA按照质量比为1：2.3放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成共混物b。S303: Put PBAT-g-GMA and PLA into an internal mixer or a twin-screw extruder at a mass ratio of 1:2.3, and melt blend for 5 minutes at a melt blending temperature of 180°C and a rotational speed of 80 rpm, Blend b is formed.
S304：共混物a与共混物b按照质量比为20:80放入密炼机或双螺杆挤出机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PLA、PBAT-g-GMA、TPS配比为63:27:10的PLA/PBAT-g-GMA/TPS复合材料。S304: Put blend a and blend b into an internal mixer or a twin-screw extruder at a mass ratio of 20:80, and melt blend for 5 minutes at a melt blending temperature of 180°C and a rotational speed of 80 rpm. PLA/PBAT-g-GMA/TPS composites with PLA, PBAT-g-GMA, and TPS ratios of 63:27:10 were formed.
对比例1Comparative example 1
将PBAT-g-GMA与PLA按照质量比为22/78的比例放入密炼机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PBAT-g-GMA/PLA复合材料。Put PBAT-g-GMA and PLA into the internal mixer according to the mass ratio of 22/78, and melt blend for 5min at the melt blending temperature of 180°C and the rotation speed of 80rpm to form PBAT-g-GMA /PLA composite material.
对比例2Comparative example 2
将PBAT-g-GMA与PLA按照质量比为24/76的比例放入密炼机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PBAT-g-GMA/PLA复合材料。Put PBAT-g-GMA and PLA into the internal mixer according to the mass ratio of 24/76, and melt blend for 5min at the melt blending temperature of 180°C and the speed of 80rpm to form PBAT-g-GMA /PLA composite material.
对比例3Comparative example 3
将PBAT-g-GMA与PLA按照质量比为30/70的比例放入密炼机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PBAT-g-GMA/PLA复合材料。Put PBAT-g-GMA and PLA into the internal mixer according to the mass ratio of 30/70, and melt blend for 5min under the conditions of melt blending temperature of 180°C and rotation speed of 80rpm to form PBAT-g-GMA /PLA composite material.
对比例4Comparative example 4
将PLA、PBAT-g-GMA和TPS按照质量比为70/20/10的比例同时放入密炼机中，在熔融共混温度为180℃、转速为80rpm的条件下熔融共混5min，形成PLA/PBAT-g-GMA/TPS复合材料。Put PLA, PBAT-g-GMA and TPS into the internal mixer at the same time according to the mass ratio of 70/20/10, and melt blend for 5 minutes at the melt blending temperature of 180 °C and the rotation speed of 80 rpm to form PLA/PBAT-g-GMA/TPS composites.
对PLA、实施例1-3和对比例1-4所制备的复合材料进行缺口冲击强度测试，测试结果如表1所示。Notched impact strength tests were performed on the composite materials prepared by PLA, Examples 1-3 and Comparative Examples 1-4, and the test results are shown in Table 1.
表1：实施例1-3和对比例1-4所制备的复合材料进行缺口冲击强度测试结果Table 1: Notched impact strength test results of the composite materials prepared in Examples 1-3 and Comparative Examples 1-4
从表1中可见，加入TPS复合材料后，复合材料的缺口冲击强度比未加入TPS的复合材料的提高了34％，是纯PLA的16倍。由实施例1和对比例4比较可见，相对于对比例4中一步法制备的复合材料的缺口冲击强度，实施例1制备得到的复合材料的缺口冲击强度提升8倍。由实施例1-3可见，当PLA、PBAT-g-GMA和TPS配比为63/27/10时，复合材料的缺口冲击强度最大。It can be seen from Table 1 that after adding the TPS composite material, the notched impact strength of the composite material is 34% higher than that of the composite material without adding TPS, which is 16 times that of pure PLA. From the comparison of Example 1 and Comparative Example 4, it can be seen that, compared with the notched impact strength of the composite material prepared by the one-step method in Comparative Example 4, the notched impact strength of the composite material prepared in Example 1 is increased by 8 times. It can be seen from Examples 1-3 that when the ratio of PLA, PBAT-g-GMA and TPS is 63/27/10, the notched impact strength of the composite material is the largest.
本领域技术人员在考虑说明书及实践这里发明的公开后，将容易想到本发明的其它实施方案。本申请旨在涵盖本发明的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明未公开的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的，本发明的真正范围和精神由下面的权利要求指出。Other embodiments of the invention will be readily apparent to those skilled in the art from consideration of the specification and practice of the invention disclosure herein. This application is intended to cover any modification, use or adaptation of the present invention, these modifications, uses or adaptations follow the general principles of the present invention and include common knowledge or conventional technical means in the technical field not disclosed in the present invention . The specification and examples are to be considered exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
应当理解的是，诸如“第一”和“第二”等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。本发明并不局限于上面已经描述的精确结构，并且可以在不脱离其范围进行各种修改和改变。本发明的范围仅由所附的权利要求来限制。It should be understood that relational terms such as "first" and "second", etc., are only used to distinguish one entity or operation from another and do not necessarily require or imply a relationship between these entities or operations. There is no such actual relationship or order between them. The present invention is not limited to the precise structure that has been described above, and various modifications and changes can be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
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