WO2017167135A1 - Graphene microsheet master batch for enhancing bioplastic and preparation method thereof - Google Patents

Graphene microsheet master batch for enhancing bioplastic and preparation method thereof Download PDF

Info

Publication number
WO2017167135A1
WO2017167135A1 PCT/CN2017/078109 CN2017078109W WO2017167135A1 WO 2017167135 A1 WO2017167135 A1 WO 2017167135A1 CN 2017078109 W CN2017078109 W CN 2017078109W WO 2017167135 A1 WO2017167135 A1 WO 2017167135A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphite
polylactic acid
graphene
graphene microchip
parts
Prior art date
Application number
PCT/CN2017/078109
Other languages
French (fr)
Chinese (zh)
Inventor
陈庆
曾军堂
叶任海
陈兵
Original Assignee
成都新柯力化工科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 成都新柯力化工科技有限公司 filed Critical 成都新柯力化工科技有限公司
Publication of WO2017167135A1 publication Critical patent/WO2017167135A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • Graphene is a two-dimensional carbon nanomaterial composed of one layer of carbon atoms. It is the thinnest two-dimensional material known at present, and its thickness is only 0.335 nm. It is composed of a hexagonal lattice and can be regarded as It is a layer of peeled graphite sheet. Graphene has excellent structural rigidity, which makes graphene have a very broad development prospect. The use of graphene miscellaneous polymer materials has become a research hotspot in the field of functional polymer materials.
  • This embodiment includes the following steps:
  • the tin stearate, 1 part by weight of the alkylene glycol and 1 part by weight of the ethylene-vinyl acetate copolymer are added to the solvent to control the temperature of the polycondensation reaction to 220 ° C, initiate the polycondensation reaction of the lactic acid monomer, and increase the graphite layer. With the gap between the layers, the interaction between the graphite layers is reduced, and an alternating laminated composite of graphene microchips/polylactic acid polymers is obtained. Stone The ene microchip/polylactic acid polymer composite material is taken out from acetone and sliced to obtain a graphene microchip/polylactic acid polymer composite microchip layer thickness of 9-10 mm.
  • a lactic acid monomer and a surfactant sodium lauryl sulfate were dissolved in an acetone solvent, and 46 parts by weight of flake graphite was immersed in acetone, wherein vinyl triethoxysilane and The weight percentage of lactic acid monomer and acetone is 0.05: 34.95: 65. After standing for 12 hours, the lactic acid monomer is transported between the graphite layer and the layer by acetone to obtain modified graphite, and 0.5 part by weight of the polycondensation initiator is obtained.

Abstract

Disclosed in the present invention are a graphene microsheet master batch for enhancing bioplastics and a preparation method thereof. The graphene microsheet/polylactic acid composite master batch is obtained by conveying lactic acid monomers between graphite layers by means of a solvent to obtain modified graphite, adding a polycondensation initiator, subjecting the lactic acid monomers to a polymerization reaction to obtain polylactic acid macromolecules between the graphite layers in situ, such that the distance between the graphite layers is increased and the acting force between the graphite layers is reduced, and subjecting the obtained alternately stacked composite materials of graphene microsheet/polylactic acid macromolecules to shearing, stripping, extrusion and pelletization. As cheap graphite is employed as a raw material in the present invention, the production cost can be effectively reduced, and the obtained master batch is of an alternately stacked and wrapped structure of graphene microsheets and polylactic acid, such that the master batch has the flexibility and the excellent mechanical performance of graphene, and thus can improve the defects of bioplastics, namely that they have low strength, poor high-temperature resistance and poor hot workability.

Description

说明书 发明名称：一种用于增强生物塑料的石墨烯微片母料及制备方法 技术领域  Description: A graphene microchip masterbatch for reinforcing bioplastics and a preparation method thereof
[0001] 本发明涉及纳米材料制备技术领域， 特别涉及一种用于增强生物塑料的石墨烯 微片母料及制备方法。  [0001] The present invention relates to the field of nano material preparation technology, and in particular to a graphene microchip masterbatch for reinforcing bioplastics and a preparation method thereof.
背景技术  Background technique
[0002] 生物降解塑料是一种可迅速地被酶或微生物分解的高分子物质。 生物降解塑料 自八十年代问世以来， 一直成为新材料研究的热点问题。 目前我国主导的生物 降解塑料利用淀粉幵发出来， 是理想的绿色高分子材料可替代以石油为原料的 塑料， 成本仅为石油塑料原料的 1/5。 随着生物塑料技术的不断发展， 生物降解 塑料中淀粉的用量也在不断提高， 降解率越来越高。 但是， 由于纯聚乳酸树脂 材质脆， 加工热稳定性差， 限制了其作为工程塑料的应用。 如何对聚乳酸树脂 进行增强， 成为本行业的新课题。  [0002] A biodegradable plastic is a high molecular substance that can be rapidly decomposed by an enzyme or a microorganism. Biodegradable plastics have been a hot issue in new materials research since its inception in the 1980s. At present, China's leading biodegradable plastics are produced by using starch, which is an ideal green polymer material that can replace petroleum-based plastics. The cost is only one-fifth of that of petroleum plastics. With the continuous development of bioplastics technology, the amount of starch in biodegradable plastics is also increasing, and the degradation rate is getting higher and higher. However, since the pure polylactic acid resin is brittle and has poor processing heat stability, it is limited to its application as an engineering plastic. How to enhance polylactic acid resin has become a new topic in the industry.
[0003] 石墨烯是由一层碳原子组成的二维碳纳米材料， 是目前已知最薄的二维材料， 其厚度仅为 0.335nm， 它由六边形的晶格组成， 可以看作是一层被剥离的石墨片 层。 石墨烯具有优异的结构刚性， 使石墨烯拥有十分广阔的发展前景。 而使用 石墨烯惨杂高分子材料在功能高分子材料领域已越来越成为研究热点。  [0003] Graphene is a two-dimensional carbon nanomaterial composed of one layer of carbon atoms. It is the thinnest two-dimensional material known at present, and its thickness is only 0.335 nm. It is composed of a hexagonal lattice and can be regarded as It is a layer of peeled graphite sheet. Graphene has excellent structural rigidity, which makes graphene have a very broad development prospect. The use of graphene miscellaneous polymer materials has become a research hotspot in the field of functional polymer materials.
[0004] 中国专利公幵号 103467943A提供了一种玻璃纤维增强聚乳酸生物塑料， 由下述 组分按重量份组成： 聚乳酸树脂 50-70份， 玻璃纤维 30-50份， 偶联剂 0.6-1.0份。 本发明的玻璃纤维增强聚乳酸生物塑料， 提高了聚乳酸树脂的力学性能。 但该 法的缺点在于玻璃纤维表面光滑， 需要通过改性才能与聚乳酸树脂键合形成增 强作用， 而玻璃纤维柔顺性差， 没有改善聚乳酸树脂的加工性能。  [0004] Chinese Patent Publication No. 103467943A provides a glass fiber reinforced polylactic acid bioplastic composed of the following components in parts by weight: 50-70 parts of polylactic acid resin, 30-50 parts of glass fiber, coupling agent 0.6 -1.0 parts. The glass fiber reinforced polylactic acid bioplastic of the invention improves the mechanical properties of the polylactic acid resin. However, the disadvantage of this method is that the surface of the glass fiber is smooth and needs to be modified to bond with the polylactic acid resin to form an enhancement effect, while the glass fiber is poor in flexibility and does not improve the processing property of the polylactic acid resin.
[0005] 中国专利公幵号 102030830A公幵了竹纤维纳米晶增强生物复合材料及其制备方 法。 将淀粉或者蛋白质基体材料加入甘油 /水中， 在 30-80°C条件下搅拌均匀， 加 入上述竹纤维纳米晶悬浮液， 继续搅拌 0.5-3小吋后， 放入模具中在 30-80°C条件 下流延成型。 纳米晶的加入大大提高了生物材料的力学强度。 本方法利用可再 生资源制备可降解材料， 成本低廉， 合成工艺简单， 合成过程绿色无污染， 所 得的产品绿色环保， 而且具有良好的生物相容性。 但是， 该方法竹纤维制备工 艺复杂， 制备周期长， 使用设备昂贵， 而且竹纤维纳米晶在生物材料中的分散 也难做到均匀分布， 可能导致成品率低。 [0005] Chinese Patent Publication No. 102030830A discloses a bamboo fiber nanocrystalline reinforcing biocomposite and a preparation method thereof. Add the starch or protein matrix material to glycerin/water, stir evenly at 30-80 °C, add the above bamboo fiber nanocrystal suspension, continue to stir for 0.5-3 吋, and put into the mold at 30-80 °C. Cast molding under conditions. The addition of nanocrystals greatly increases the mechanical strength of biomaterials. The method utilizes renewable resources to prepare degradable materials, has low cost, simple synthesis process, and green pollution-free synthesis process. The products obtained are environmentally friendly and have good biocompatibility. However, the bamboo fiber preparation process is complicated, the preparation cycle is long, the equipment used is expensive, and the dispersion of the bamboo fiber nanocrystals in the biological material is difficult to uniformly distribute, which may result in low yield.
[0006] 中国专利公幵号 101484628公幵了一种提高纤维的强度和刚度的方法。 该方法 将石墨烯片粘附至碳丝束或纱线之中或之上以形成改性纤维， 其中纳米增强材 料粘附或截留在碳丝束中。 改性的树脂纤维相对于未改性树脂的纤维刚度和强 度性能提高显著， 但是石墨烯的成本较高， 不利于大规模生产推广。  [0006] Chinese Patent Publication No. 101,484, 628 discloses a method of increasing the strength and stiffness of fibers. The method adheres a graphene sheet to or into a carbon tow or yarn to form a modified fiber, wherein the nano-reinforced material adheres or is trapped in the carbon tow. The fiber stiffness and strength properties of the modified resin fiber are significantly improved relative to the unmodified resin, but the cost of graphene is high, which is not conducive to mass production promotion.
[0007] 综上所述， 现有技术中还没有一种生产原料成本低廉， 并且能够有效改善生物 塑料低强度、 耐高温性差、 热加工性差的缺陷的技术手段。 [0007] In summary, there is no technical means in the prior art for producing raw materials which are low in cost and capable of effectively improving the defects of low strength, high temperature resistance and poor hot workability of bioplastics.
技术问题  technical problem
[0008] 生物塑料低强度、 耐高温性差、 热加工性差的缺陷。  [0008] Bioplastics have the disadvantages of low strength, poor high temperature resistance, and poor hot workability.
问题的解决方案  Problem solution
技术解决方案  Technical solution
[0009] 为了解决上述方法的不足和缺陷， 本发明幵发出一种用于增强生物塑料的石墨 烯微片母料及制备方法。 本发明通过溶剂将乳酸单体输送到石墨层与层之间， 静置一预设吋间， 获得改性石墨， 再加入缩聚反应引发剂， 将乳酸单体通过聚 合反应在石墨层间原位获得聚乳酸高分子， 增大石墨层间距离， 降低石墨层间 作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠层复合材料， 而后通过施加剪 切力作用于石墨烯微片 /聚乳酸高分子的交替叠层复合材料， 自然冷却得到初级 石墨烯聚乳酸复合母料， 而后通过螺杆挤出机剪切剥离、 挤出造粒得到石墨烯 聚乳酸复合母料。  In order to solve the deficiencies and shortcomings of the above methods, the present invention emits a graphene microchip masterbatch for reinforcing bioplastics and a preparation method thereof. The invention transports the lactic acid monomer to the graphite layer and the layer through a solvent, and stands still between the predetermined turns to obtain the modified graphite, and then adds the polycondensation reaction initiator to pass the lactic acid monomer through the polymerization reaction between the graphite layers. Obtaining polylactic acid polymer, increasing the distance between graphite layers, reducing the interaction between graphite layers, obtaining an alternating laminated composite of graphene microchips/polylactic acid polymers, and then applying shearing force to graphene microchips/ The alternating laminated composite material of polylactic acid polymer is naturally cooled to obtain a primary graphene polylactic acid composite master batch, and then sheared and peeled by a screw extruder, and extruded and granulated to obtain a graphene polylactic acid composite master batch.
[0010] 一方面， 本发明提供一种用于增强生物塑料的石墨烯微片母料， 所述母料由包 括如下重量份数的原料制备而成：  In one aspect, the present invention provides a graphene microchip masterbatch for reinforcing bioplastics, the masterbatch being prepared from a raw material comprising the following parts by weight:
[0011] 石墨 32-46份，  [0011] 32-46 parts of graphite,
[0012] 乳酸单体 50-66份，  [0012] 50-66 parts of lactic acid monomer,
[0013] 增塑剂 1-2份，  [0013] 1-2 parts of plasticizer,
[0014] 增容剂 1-2份，  [0014] 1-2 parts of compatibilizer,
[0015] 其中， 所述石墨为致密结晶状石墨， 鳞片石墨、 膨胀石墨或可膨胀石墨中的一 种或几种， 所述增容剂为乙烯 -醋酸乙烯共聚物、 乙烯 -丙烯酸共聚物中的至少一 种， 所述增塑剂为亚烷基二醇。 [0015] wherein the graphite is dense crystalline graphite, one of flake graphite, expanded graphite or expandable graphite The compatibilizer is at least one of an ethylene-vinyl acetate copolymer and an ethylene-acrylic acid copolymer, and the plasticizer is an alkylene glycol.
[0016] 可选的， 所述母料的结构为石墨烯微片与聚乳酸交替叠层包裹结构。  [0016] Optionally, the structure of the master batch is an alternating laminate structure of graphene microchips and polylactic acid.
[0017] 另一方面， 本发明提供一种剥离石墨制备石墨烯的方法， 所述方法包括以下步 骤： [0017] In another aspect, the present invention provides a method of exfoliating graphite to produce graphene, the method comprising the steps of:
[0018] 一种用于增强生物塑料的石墨烯微片母料的制备方法， 所述方法包括以下步骤  [0018] A method for preparing a graphene microchip masterbatch for reinforcing bioplastics, the method comprising the following steps
[0019] a.将 50-66份乳酸单体与适量表面活性剂溶入溶剂中， 再将 32-46份石墨浸没在 所述溶剂中， 通过所述溶剂将所述乳酸单体输送到石墨层与层之间， 静置一预 设吋间后， 获得改性石墨； [0019] a 50-66 parts of lactic acid monomer and an appropriate amount of surfactant dissolved in a solvent, and then 32-46 parts of graphite immersed in the solvent, the lactic acid monomer is transported to the graphite by the solvent Between the layers, after standing at a predetermined turn, obtaining modified graphite;
[0020] b.将 0-1重量份缩聚反应引发剂、 1-2重量份增塑剂和 1-2重量份增溶剂加入溶剂 中， 引发乳酸单体发生缩聚反应， 增加石墨层与层之间的间隙， 降低石墨层间 作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠层复合材料；  [0020] b 0-1 parts by weight of a polycondensation reaction initiator, 1-2 parts by weight of a plasticizer and 1-2 parts by weight of a solubilizer added to the solvent, triggering the polycondensation reaction of the lactic acid monomer, increasing the graphite layer and layer The gap between the layers reduces the interaction between the graphite layers to obtain an alternating laminated composite of graphene microchip/polylactic acid polymer;
[0021] c.将所述石墨烯微片 /聚乳酸高分子复合材料从所述溶剂中取出烘干进行切片处 理， 将获得的石墨烯微片 /聚乳酸高分子复合材料微片加入密炼式三螺杆挤出机 ， 设置挤出温度为 100-120°C， 剪切剥离、 挤出造粒石墨烯微片 /聚乳酸复合母料  [0021] c the graphene microchip / polylactic acid polymer composite material is taken out from the solvent and dried for slicing, the obtained graphene microchip / polylactic acid polymer composite microchip is added to the refining Three-screw extruder, set extrusion temperature of 100-120 ° C, shear stripping, extrusion granulation graphene microchip / polylactic acid composite masterbatch
[0022] 可选的， 所述表面活性剂为乙烯基三甲氧基硅烷、 乙烯基三乙氧基硅、 十二烷 基硫酸钠、 十二烷基磺酸钠和聚乙烯吡咯烷酮中的一种或几种， 所述溶剂为甲 醇、 乙醇、 丙酮中的一种或几种， 所述增容剂为乙烯 -醋酸乙烯共聚物、 乙烯-丙 烯酸共聚物中的至少一种， 所述增塑剂为亚烷基二醇。 [0022] Optionally, the surfactant is one of vinyl trimethoxysilane, vinyl triethoxysilane, sodium lauryl sulfate, sodium dodecyl sulfate, and polyvinylpyrrolidone Or the solvent is one or more of methanol, ethanol, and acetone, and the compatibilizer is at least one of an ethylene-vinyl acetate copolymer and an ethylene-acrylic acid copolymer, the plasticizer It is an alkylene glycol.
[0023] 可选的， 所述表面活性剂、 所述乳酸单体和所述溶剂的重量百分比为 0.05-0.2 ： 34.95-44.8： 55-65。  [0023] Optionally, the weight percentage of the surfactant, the lactic acid monomer and the solvent is 0.05-0.2: 34.95-44.8: 55-65.
[0024] 可选的， 在步骤 b中， 在所述引发乳酸单体发生缩聚反应吋加入缩聚反应引发 齐 ij， 所述缩聚反应引发剂为锡、 铅、 锌、 钛、 锗、 锰、 镁及稀土类元素中的至 少一种金属的脂肪酸盐、 碳酸盐、 硫酸盐、 磷酸盐、 氧化物、 氢氧化物、 醇盐  [0024] Optionally, in the step b, the polycondensation reaction is initiated in the polycondensation reaction of the initiating lactic acid monomer, and the polycondensation initiator is tin, lead, zinc, titanium, antimony, manganese, magnesium. And fatty acid salts, carbonates, sulfates, phosphates, oxides, hydroxides, alkoxides of at least one of the rare earth elements
[0025] 可选的， 控制所述缩聚反应的温度为 100-220°C。 [0026] 可选的， 在步骤 c中， 将所述石墨烯微片 /聚乳酸高分子复合材料从所述溶剂中 取出烘干进行切片处理后， 获得石墨烯微片 /聚乳酸高分子复合材料微片片层厚 度为 5-10mm。 [0025] Optionally, the temperature for controlling the polycondensation reaction is 100-220 °C. [0026] Optionally, in step c, the graphene microchip/polylactic acid polymer composite material is taken out from the solvent and dried for slicing, and then the graphene microchip/polylactic acid polymer composite is obtained. The material microchip layer thickness is 5-10 mm.
发明的有益效果  Advantageous effects of the invention
有益效果  Beneficial effect
[0027] 本申请技术方案， 至少具有如下一种或多种技术效果：  [0027] The technical solution of the present application has at least one or more of the following technical effects:
[0028] 1、 本发明采用乳酸单体作为生产原料不仅作为石墨材料的剥离剂， 而且石墨 烯微片与聚乳酸高分子的交替叠层包裹， 制备的在母料颗粒中石墨烯微片能够 在聚乳酸高分子均匀分布， 进而能够利用石墨烯的柔顺性和优异的机械性能， 提高生物材料的强度、 耐高温和加工性能。  [0028] 1. The invention adopts a lactic acid monomer as a raw material for production, not only as a stripping agent for a graphite material, but also an alternating lamination of a graphene microchip and a polylactic acid polymer, and the prepared graphene microchip can be prepared in the master batch particle. The polylactic acid polymer is uniformly distributed, and the flexibility, high temperature resistance, and processability of the biomaterial can be improved by utilizing the flexibility of the graphene and excellent mechanical properties.
[0029] 2、 本发明采用乳酸单体发生缩聚反应在石墨层间原位合成聚乳酸并且获得石 墨烯微片， 使用了常规的生物塑料和石墨作为原材料， 降低了母料生产成本。 实施该发明的最佳实施例 2. The present invention employs a polycondensation reaction of a lactic acid monomer to synthesize polylactic acid in situ between graphite layers and obtain a graphene microchip, which uses conventional bioplastics and graphite as raw materials, thereby reducing the production cost of the master batch. BEST MODE FOR CARRYING OUT THE INVENTION
本发明的最佳实施方式  BEST MODE FOR CARRYING OUT THE INVENTION
[0030] 通过具体实施方式对本发明作进一步的详细说明， 但不应将此理解为本发明的 范围仅限于以下的实例。 在不脱离本发明上述方法思想的情况下， 根据本领域 普通技术知识和惯用手段做出的各种替换或变更， 均应包含在本发明的范围内 The present invention is further described in detail with reference to the preferred embodiments thereof, but the scope of the invention should not be construed as limited. Various substitutions or modifications made in accordance with the ordinary skill in the art and the conventional means are included in the scope of the present invention without departing from the spirit and scope of the invention.
本发明的实施方式 Embodiments of the invention
[0031] 实施例一 [0031] Embodiment 1
[0032] 本实施例包括如下步骤： [0032] This embodiment includes the following steps:
[0033] 将 66重量份的乳酸单体和表面活性剂乙烯基三甲氧基硅烷溶入甲醇溶剂中， 再 将 32重量份的膨胀石墨浸没在甲醇中， 其中， 乙烯基三甲氧基硅与乳酸单体和 甲醇的重量百分比为 0.05 : 34.95： 65， 静置 12小吋后， 通过甲醇将乳酸单体输 送到石墨层与层之间， 获得改性石墨， 将 0.5重量份缩聚反应引发剂硬脂酸锡、 1 重量份的亚烷基二醇和 1重量份的乙烯-醋酸乙烯共聚物加入溶剂中， 控制缩聚反 应的温度为 100°C， 引发乳酸单体发生缩聚反应， 增加石墨层与层之间的间隙， 降低石墨层间作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠层复合材料。 将 石墨烯微片 /聚乳酸高分子复合材料从甲醇中取出烘干进行切片处理， 获得石墨 烯微片 /聚乳酸高分子复合材料微片片层厚度为 5-6mm。 将获得的石墨烯微片 /聚 乳酸高分子复合材料微片加入密炼式三螺杆挤出机， 设置挤出温度为 100°C， 挤 出造粒， 自然冷却得到初级石墨烯聚乳酸复合母料。 [0033] 66 parts by weight of a lactic acid monomer and a surfactant vinyltrimethoxysilane were dissolved in a methanol solvent, and 32 parts by weight of expanded graphite was immersed in methanol, wherein vinyltrimethoxysilane and lactic acid were used. The weight percentage of monomer and methanol is 0.05 : 34.95: 65. After standing for 12 hours, the lactic acid monomer is transported between the graphite layer and the layer by methanol to obtain modified graphite, and 0.5 part by weight of the polycondensation initiator is hard. Tin strontium, 1 part by weight of alkylene glycol and 1 part by weight of ethylene-vinyl acetate copolymer are added to the solvent to control polycondensation The temperature should be 100 °C, the polycondensation reaction of the lactic acid monomer is initiated, the gap between the graphite layer and the layer is increased, and the interaction between the graphite layers is reduced to obtain an alternating laminated composite material of the graphene microchip/polylactic acid polymer. The graphene microchip/polylactic acid polymer composite material was taken out from methanol and dried for slicing to obtain a graphene microchip/polylactic acid polymer composite microchip sheet having a thickness of 5-6 mm. The obtained graphene microchip/polylactic acid polymer composite microchip is added to a close-mixing three-screw extruder, and the extrusion temperature is set to 100 ° C, extrusion granulation, and natural cooling to obtain a primary graphene polylactic acid composite mother. material.
[0034] 实施例二  [0034] Embodiment 2
[0035] 本实施例包括如下步骤：  [0035] This embodiment includes the following steps:
[0036] 将 66重量份的乳酸单体和表面活性剂乙烯基三乙氧基硅溶入丙酮溶剂中， 再将 32重量份的膨胀石墨浸没在丙酮中， 其中， 乙烯基三乙氧基硅与乳酸单体和丙 酮的重量百分比为 0.05 : 34.95： 65， 静置 12小吋后， 通过丙酮将乳酸单体输送 到石墨层与层之间， 获得改性石墨， 将 0.5重量份缩聚反应引发剂硬脂酸锡、 1重 量份的亚烷基二醇和 1重量份的乙烯-丙烯酸共聚物加入溶剂中， 控制缩聚反应的 温度为 100°C， 引发乳酸单体发生缩聚反应， 增加石墨层与层之间的间隙， 降低 石墨层间作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠层复合材料。 将石墨 烯微片 /聚乳酸高分子复合材料从丙酮中取出烘干进行切片处理， 获得石墨烯微 片 /聚乳酸高分子复合材料微片片层厚度为 5-6mm。 将获得的石墨烯微片 /聚乳酸 高分子复合材料微片加入密炼式三螺杆挤出机， 设置挤出温度为 100°C， 挤出造 粒， 自然冷却得到初级石墨烯聚乳酸复合母料。 [0036] 66 parts by weight of a lactic acid monomer and a surfactant vinyltriethoxysilane were dissolved in an acetone solvent, and 32 parts by weight of expanded graphite was immersed in acetone, wherein vinyltriethoxysilane The weight percentage of lactic acid monomer and acetone is 0.05 : 34.95: 65. After standing for 12 hours, the lactic acid monomer is transported between the graphite layer and the layer through acetone to obtain modified graphite, which is initiated by 0.5 part by weight of polycondensation reaction. The tin stearate, 1 part by weight of the alkylene glycol and 1 part by weight of the ethylene-acrylic acid copolymer are added to the solvent to control the temperature of the polycondensation reaction to 100 ° C, the polycondensation reaction of the lactic acid monomer is initiated, and the graphite layer is increased. The gap between the layers reduces the interaction between the graphite layers to obtain an alternating laminated composite of graphene microchips/polylactic acid polymers. The graphene microchip/polylactic acid polymer composite material was taken out from acetone and sliced to obtain a graphene microchip/polylactic acid polymer composite microchip layer thickness of 5-6 mm. The obtained graphene microchip/polylactic acid polymer composite microchip is added to a close-mixing three-screw extruder, and the extrusion temperature is set to 100 ° C, extrusion granulation, and natural cooling to obtain a primary graphene polylactic acid composite mother. material.
[0037] 实施例三  [0037] Embodiment 3
[0038] 本实施例包括如下步骤：  [0038] This embodiment includes the following steps:
[0039] 将 66重量份的乳酸单体和表面活性剂乙烯基三乙氧基硅溶入丙酮溶剂中， 再将 32重量份的膨胀石墨浸没在丙酮中， 其中， 乙烯基三乙氧基硅与乳酸单体和丙 酮的重量百分比为 0.05 : 34.95： 65， 静置 12小吋后， 通过丙酮将乳酸单体输送 到石墨层与层之间， 获得改性石墨， 将 0.5重量份缩聚反应引发剂硬脂酸锡、 1重 量份的亚烷基二醇和 1重量份的乙烯-醋酸乙烯共聚物加入溶剂中， 控制缩聚反应 的温度为 220°C， 引发乳酸单体发生缩聚反应， 增加石墨层与层之间的间隙， 降 低石墨层间作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠层复合材料。 将石 墨烯微片 /聚乳酸高分子复合材料从丙酮中取出烘干进行切片处理， 获得石墨烯 微片 /聚乳酸高分子复合材料微片片层厚度为 9- 10mm。 将获得的石墨烯微片 /聚乳 酸高分子复合材料微片加入密炼式三螺杆挤出机， 设置挤出温度为 100°C， 挤出 造粒， 自然冷却得到初级石墨烯聚乳酸复合母料。 [0039] 66 parts by weight of a lactic acid monomer and a surfactant vinyltriethoxysilane were dissolved in an acetone solvent, and 32 parts by weight of expanded graphite was immersed in acetone, wherein vinyltriethoxysilane The weight percentage of lactic acid monomer and acetone is 0.05 : 34.95: 65. After standing for 12 hours, the lactic acid monomer is transported between the graphite layer and the layer through acetone to obtain modified graphite, which is initiated by 0.5 part by weight of polycondensation reaction. The tin stearate, 1 part by weight of the alkylene glycol and 1 part by weight of the ethylene-vinyl acetate copolymer are added to the solvent to control the temperature of the polycondensation reaction to 220 ° C, initiate the polycondensation reaction of the lactic acid monomer, and increase the graphite layer. With the gap between the layers, the interaction between the graphite layers is reduced, and an alternating laminated composite of graphene microchips/polylactic acid polymers is obtained. Stone The ene microchip/polylactic acid polymer composite material is taken out from acetone and sliced to obtain a graphene microchip/polylactic acid polymer composite microchip layer thickness of 9-10 mm. The obtained graphene microchip/polylactic acid polymer composite microchip is added to a close-mixing three-screw extruder, and the extrusion temperature is set to 100 ° C, extrusion granulation, and natural cooling to obtain a primary graphene polylactic acid composite mother. material.
[0040] 实施例四  [0040] Embodiment 4
[0041] 本实施例包括如下步骤：  [0041] This embodiment includes the following steps:
[0042] 将 50重量份的乳酸单体和表面活性剂十二烷基硫酸钠溶入丙酮溶剂中， 再将 46 重量份的鳞片石墨浸没在丙酮中， 其中， 乙烯基三乙氧基硅与乳酸单体和丙酮 的重量百分比为 0.05 : 34.95： 65， 静置 12小吋后， 通过丙酮将乳酸单体输送到 石墨层与层之间， 获得改性石墨， 将 0.5重量份缩聚反应引发剂辛酸亚锡、 2重量 份的亚烷基二醇和 2重量份的乙烯-丙烯酸共聚物加入溶剂中， 控制缩聚反应的温 度为 220°C， 引发乳酸单体发生缩聚反应， 增加石墨层与层之间的间隙， 降低石 墨层间作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠层复合材料。 将石墨烯 微片 /聚乳酸高分子复合材料从丙酮中取出烘干进行切片处理， 获得石墨烯微片 / 聚乳酸高分子复合材料微片片层厚度为 9-10mm。 将获得的石墨烯微片 /聚乳酸高 分子复合材料微片加入密炼式三螺杆挤出机， 设置挤出温度为 120°C， 挤出造粒 ， 自然冷却得到初级石墨烯聚乳酸复合母料。  [0042] 50 parts by weight of a lactic acid monomer and a surfactant sodium lauryl sulfate were dissolved in an acetone solvent, and 46 parts by weight of flake graphite was immersed in acetone, wherein vinyl triethoxysilane and The weight percentage of lactic acid monomer and acetone is 0.05: 34.95: 65. After standing for 12 hours, the lactic acid monomer is transported between the graphite layer and the layer by acetone to obtain modified graphite, and 0.5 part by weight of the polycondensation initiator is obtained. Stannous octoate, 2 parts by weight of an alkylene glycol and 2 parts by weight of an ethylene-acrylic acid copolymer are added to the solvent to control the temperature of the polycondensation reaction to 220 ° C, which initiates a polycondensation reaction of the lactic acid monomer, and increases the graphite layer and the layer. The gap between the layers reduces the interaction between the graphite layers to obtain an alternating laminated composite of graphene microchips/polylactic acid polymers. The graphene microchip/polylactic acid polymer composite material was taken out from acetone and sliced to obtain a graphene microchip/polylactic acid polymer composite microchip sheet having a thickness of 9-10 mm. The obtained graphene microchip/polylactic acid polymer composite microchip is added to a close-mixing three-screw extruder, and the extrusion temperature is set to 120 ° C, extrusion granulation, and natural cooling to obtain a primary graphene polylactic acid composite mother. material.
[0043] 实施例五  [0043] Embodiment 5
[0044] 本实施例包括如下步骤：  [0044] This embodiment includes the following steps:
[0045] 将 50重量份的乳酸单体和表面活性剂十二烷基硫酸钠溶入丙酮溶剂中， 再将 46 重量份的鳞片石墨浸没在丙酮中， 其中， 乙烯基三乙氧基硅与乳酸单体和丙酮 的重量百分比为 0.1 ： 40： 59.9， 静置 12小吋后， 通过丙酮将乳酸单体输送到石 墨层与层之间， 获得改性石墨， 将 0.5重量份缩聚反应引发剂氯化亚锡、 1重量份 的亚烷基二醇和 2重量份的乙烯-醋酸乙烯共聚物加入溶剂中， 控制缩聚反应的温 度为 220°C， 引发乳酸单体发生缩聚反应， 增加石墨层与层之间的间隙， 降低石 墨层间作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠层复合材料。 将石墨烯 微片 /聚乳酸高分子复合材料从丙酮中取出烘干进行切片处理， 获得石墨烯微片 / 聚乳酸高分子复合材料微片片层厚度为 9-10mm。 将获得的石墨烯微片 /聚乳酸高 分子复合材料微片加入密炼式三螺杆挤出机， 设置挤出温度为 120°C， 剪切剥离 挤出造粒， 自然冷却得到初级石墨烯聚乳酸复合母料。 [0045] 50 parts by weight of a lactic acid monomer and a surfactant sodium lauryl sulfate were dissolved in an acetone solvent, and 46 parts by weight of flake graphite was immersed in acetone, wherein vinyl triethoxysilane and The weight percentage of lactic acid monomer and acetone is 0.1:40: 59.9. After standing for 12 hours, the lactic acid monomer is transported between the graphite layer and the layer through acetone to obtain modified graphite, and 0.5 part by weight of the polycondensation initiator is obtained. Stannous chloride, 1 part by weight of an alkylene glycol and 2 parts by weight of an ethylene-vinyl acetate copolymer are added to the solvent to control the temperature of the polycondensation reaction to 220 ° C, which initiates a polycondensation reaction of the lactic acid monomer, and increases the graphite layer and The gap between the layers reduces the interaction between the graphite layers to obtain an alternating laminated composite of graphene microchips/polylactic acid polymers. The graphene microchip/polylactic acid polymer composite material was taken out from acetone and subjected to slicing to obtain a graphene microchip/polylactic acid polymer composite microchip sheet having a thickness of 9-10 mm. The graphene microchip/polylactic acid will be obtained high The molecular composite microchip was added to a close-mixing three-screw extruder, and the extrusion temperature was set to 120 ° C, shear-peeled extrusion granulation, and natural cooling to obtain a primary graphene polylactic acid composite master batch.
[0046] 尽管已描述了本发明的优选实施例， 但本领域内的技术人员一旦得知了基本创 造性概念， 则可对这些实施例作出另外的变更和修改。 所以， 所附权利要求意 欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。 [0046] While the preferred embodiment of the invention has been described, it will be apparent to those skilled in Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and the modifications and
[0047] 显然， 本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的 精神和范围。 这样， 倘若本发明的这些修改和变型属于本发明权利要求及其等 同技术的范围之内， 则本发明也意图包含这些改动和变型在内。 。 [0047] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention cover the modifications and the modifications of the invention .
工业实用性  Industrial applicability
[0048] 本发明工艺简单， 制备周期短， 使用的设备成本低廉， 适合大规模生产。  [0048] The invention has simple process, short preparation period, low cost of equipment used, and is suitable for large-scale production.

Claims

权利要求书 Claim
[权利要求 1] 一种用于增强生物塑料的石墨烯微片母料， 所述母料由包括如下重量 份数的原料制备而成：  [Claim 1] A graphene microchip masterbatch for reinforcing a bioplastic, the masterbatch being prepared from a raw material comprising the following parts by weight:
石墨 32-46份，  32-46 parts of graphite,
乳酸单体 50-66份，  50-66 parts of lactic acid monomer,
增塑剂 1-2份，  Plasticizer 1-2 parts,
增容剂 1-2份，  Compatibilizer 1-2 parts,
其中， 所述石墨为致密结晶状石墨， 鳞片石墨、 膨胀石墨或可膨胀石 墨中的一种或几种， 所述增容剂为乙烯 -醋酸乙烯共聚物、 乙烯 -丙烯 酸共聚物中的至少一种， 所述增塑剂为亚烷基二醇;所述母料的结构 为石墨烯微片与聚乳酸交替叠层包裹结构。  Wherein the graphite is one or more of dense crystalline graphite, flake graphite, expanded graphite or expandable graphite, and the compatibilizer is at least one of ethylene-vinyl acetate copolymer and ethylene-acrylic acid copolymer. The plasticizer is an alkylene glycol; the masterbatch has a structure in which a graphene microchip and a polylactic acid are alternately laminated.
2、 一种用于增强生物塑料的石墨烯微片母料的制备方法， 其特征在 于， 所述方法包括以下步骤：  2. A method for preparing a graphene microchip masterbatch for reinforcing a bioplastic, characterized in that the method comprises the steps of:
a.将 50-66份乳酸单体与适量表面活性剂溶入溶剂中， 再将 32-46份石 墨浸没在所述溶剂中， 通过所述溶剂将所述乳酸单体输送到石墨层与 层之间， 静置一预设吋间后， 获得改性石墨；  a. Dissolving 50-66 parts of lactic acid monomer and an appropriate amount of surfactant into a solvent, and immersing 32-46 parts of graphite in the solvent, and transporting the lactic acid monomer to the graphite layer and layer by the solvent Between, after standing a predetermined time, obtain modified graphite;
b.将 0-1重量份缩聚反应引发剂、 1-2重量份增塑剂和 1-2重量份增溶剂 加入溶剂中， 引发乳酸单体发生缩聚反应， 增加石墨层与层之间的间 隙， 降低石墨层间作用力， 得到石墨烯微片 /聚乳酸高分子的交替叠 层复合材料；  b. 0-1 parts by weight of a polycondensation initiator, 1-2 parts by weight of a plasticizer and 1-2 parts by weight of a solubilizer are added to the solvent to initiate a polycondensation reaction of the lactic acid monomer, increasing the gap between the graphite layer and the layer , reducing the interaction between the graphite layers to obtain an alternating laminated composite material of graphene microchip/polylactic acid polymer;
c.将所述石墨烯微片 /聚乳酸高分子复合材料从所述溶剂中取出烘干 进行切片处理， 将获得的石墨烯微片 /聚乳酸高分子复合材料微片加 入密炼式三螺杆挤出机， 设置挤出温度为 100-120°C， 剪切剥离、 挤 出造粒石墨烯微片 /聚乳酸复合母料。  c. The graphene microchip/polylactic acid polymer composite material is taken out from the solvent and dried for slicing, and the obtained graphene microchip/polylactic acid polymer composite microchip is added to the dense three-screw. The extruder was set to an extrusion temperature of 100-120 ° C, shear-peeled, and extruded granulated graphene microchip/polylactic acid composite master batch.
3、 根据权利要求 2所述的一种用于增强生物塑料的石墨烯微片母料的 制备方法， 其特征在于， 所述表面活性剂为乙烯基三甲氧基硅烷、 乙 烯基三乙氧基硅、 十二烷基硫酸钠、 十二烷基磺酸钠和聚乙烯吡咯烷 酮中的一种或几种， 所述溶剂为甲醇、 乙醇、 丙酮中的一种或几种， 所述增容剂为乙烯 -醋酸乙烯共聚物、 乙烯 -丙烯酸共聚物中的至少一 种， 所述增塑剂为亚烷基二醇。 3. A method for preparing a graphene microchip masterbatch for reinforcing bioplastics according to claim 2, wherein the surfactant is vinyltrimethoxysilane or vinyltriethoxylate. One or more of silicon, sodium lauryl sulfate, sodium dodecyl sulfate, and polyvinylpyrrolidone, and the solvent is one or more of methanol, ethanol, and acetone. The compatibilizer is at least one of an ethylene-vinyl acetate copolymer and an ethylene-acrylic acid copolymer, and the plasticizer is an alkylene glycol.
4、 根据权利要求 2所述的一种用于增强生物塑料的石墨烯微片母料的 制备方法， 其特征在于， 所述表面活性剂、 所述乳酸单体和所述溶剂 的重量百分比为 0.05-0.2 : 34.95-44.8： 55-65。 4. The method for preparing a graphene microchip masterbatch for reinforcing bioplastics according to claim 2, wherein a weight percentage of the surfactant, the lactic acid monomer, and the solvent is 0.05-0.2 : 34.95-44.8: 55-65.
5、 根据权利要求 2所述的一种用于增强生物塑料的石墨烯微片母料的 制备方法， 其特征在于， 在步骤 b中， 在所述引发乳酸单体发生缩聚 反应吋加入缩聚反应引发剂， 所述缩聚反应引发剂为锡、 铅、 锌、 钛 、 锗、 锰、 镁及稀土类元素中的至少一种金属的脂肪酸盐、 碳酸盐、 硫酸盐、 磷酸盐、 氧化物、 氢氧化物、 醇盐。  The method for preparing a graphene microchip masterbatch for reinforcing bioplastics according to claim 2, wherein in step b, a polycondensation reaction is carried out after the initiating polycondensation reaction of the lactic acid monomer An initiator, the polycondensation initiator is a fatty acid salt, a carbonate, a sulfate, a phosphate, an oxide of at least one of tin, lead, zinc, titanium, lanthanum, manganese, magnesium, and a rare earth element , hydroxide, alkoxide.
6、 根据权利要求 2所述的一种用于增强生物塑料的石墨烯微片母料的 制备方法， 其特征在于， 控制所述缩聚反应的温度为 100-220°C。 6. A method of preparing a graphene microchip masterbatch for reinforcing bioplastics according to claim 2, wherein the temperature for controlling the polycondensation reaction is from 100 to 220 °C.
7、 根据权利要求 2所述的一种用于增强生物塑料的石墨烯微片母料的 制备方法， 其特征在于， 在步骤 c中， 将所述石墨烯微片 /聚乳酸高分 子复合材料从所述溶剂中取出烘干进行切片处理后， 获得石墨烯微片 /聚乳酸高分子复合材料微片片层厚度为 5-10mm。 7. The method for preparing a graphene microchip masterbatch for reinforcing bioplastics according to claim 2, wherein in step c, the graphene microchip/polylactic acid polymer composite material is used. After the film is taken out from the solvent and subjected to slicing, the thickness of the graphene microchip/polylactic acid polymer composite microsheet is 5-10 mm.
PCT/CN2017/078109 2016-03-30 2017-03-24 Graphene microsheet master batch for enhancing bioplastic and preparation method thereof WO2017167135A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610189912.7 2016-03-30
CN201610189912.7A CN105754310A (en) 2016-03-30 2016-03-30 Graphene nanoplatelet master batch for enhancing bioplastics and preparation method

Publications (1)

Publication Number Publication Date
WO2017167135A1 true WO2017167135A1 (en) 2017-10-05

Family

ID=56346725

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/078109 WO2017167135A1 (en) 2016-03-30 2017-03-24 Graphene microsheet master batch for enhancing bioplastic and preparation method thereof

Country Status (2)

Country Link
CN (1) CN105754310A (en)
WO (1) WO2017167135A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105754310A (en) * 2016-03-30 2016-07-13 成都新柯力化工科技有限公司 Graphene nanoplatelet master batch for enhancing bioplastics and preparation method

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167894A (en) * 2011-01-24 2011-08-31 中国科学院长春应用化学研究所 Graphene/polylactic acid composite material and preparation method thereof
CN103086367A (en) * 2013-01-16 2013-05-08 天津工业大学 Preparation method of polylactic acid functionalized graphene
CN103772975A (en) * 2012-10-25 2014-05-07 黑龙江鑫达企业集团有限公司 Graphene/polymer conductive composite material
CN103804661A (en) * 2014-01-22 2014-05-21 盐城菁华新材料科技有限公司 Graphene/polylactic acid composite material and preparation method thereof
CN104559228A (en) * 2014-12-30 2015-04-29 西南科技大学 Preparation method of graphene oxide reinforced leather solid waste collagen powder/polylactic acid composite
WO2015170344A1 (en) * 2014-05-09 2015-11-12 Council Of Scientific & Industrial Research An improved next generation off-laboratory polymer chip electrode
JP2015214611A (en) * 2014-05-08 2015-12-03 東レ株式会社 Film containing polylactic acid-based resin
CN105331062A (en) * 2014-07-15 2016-02-17 中国石油化工股份有限公司 Carbon nanotube / polylactic acid conductive composite material and preparation method thereof
CN105754310A (en) * 2016-03-30 2016-07-13 成都新柯力化工科技有限公司 Graphene nanoplatelet master batch for enhancing bioplastics and preparation method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101037498A (en) * 2006-03-17 2007-09-19 上海杰事杰新材料股份有限公司 Microencapsulation reinforced inorganic particle and preparation method thereof
CN101407637B (en) * 2008-11-21 2011-07-27 华东理工大学 Fiber reinforced composite material and preparation thereof
EP2468812A1 (en) * 2010-12-21 2012-06-27 Basf Se Thermoplastic moulding material

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167894A (en) * 2011-01-24 2011-08-31 中国科学院长春应用化学研究所 Graphene/polylactic acid composite material and preparation method thereof
CN103772975A (en) * 2012-10-25 2014-05-07 黑龙江鑫达企业集团有限公司 Graphene/polymer conductive composite material
CN103086367A (en) * 2013-01-16 2013-05-08 天津工业大学 Preparation method of polylactic acid functionalized graphene
CN103804661A (en) * 2014-01-22 2014-05-21 盐城菁华新材料科技有限公司 Graphene/polylactic acid composite material and preparation method thereof
JP2015214611A (en) * 2014-05-08 2015-12-03 東レ株式会社 Film containing polylactic acid-based resin
WO2015170344A1 (en) * 2014-05-09 2015-11-12 Council Of Scientific & Industrial Research An improved next generation off-laboratory polymer chip electrode
CN105331062A (en) * 2014-07-15 2016-02-17 中国石油化工股份有限公司 Carbon nanotube / polylactic acid conductive composite material and preparation method thereof
CN104559228A (en) * 2014-12-30 2015-04-29 西南科技大学 Preparation method of graphene oxide reinforced leather solid waste collagen powder/polylactic acid composite
CN105754310A (en) * 2016-03-30 2016-07-13 成都新柯力化工科技有限公司 Graphene nanoplatelet master batch for enhancing bioplastics and preparation method

Also Published As

Publication number Publication date
CN105754310A (en) 2016-07-13

Similar Documents

Publication Publication Date Title
KR101712506B1 (en) Manufacturing Method of Filament for 3D Print and Filament
CN109456555A (en) A kind of water-soluble polyvinyl alcohol film of blow molding and its preparation method and application
CN100480278C (en) Polymer/organic montmorillonite nano composite flame-proof masterbatch, and preparing method and application thereof
TW200813143A (en) Biodegradable resin composition with improved toughness and thermal resistance and production method thereof
CN105647137A (en) 3D printing polylactic acid /leather powder composite materials and preparation method thereof
WO2012000141A1 (en) Thermoplastic resin composite material modified with non-metallic material and product manufacturing method using the same
CN107474423A (en) A kind of formula of high heat resistant plastice section bar
CN102604294A (en) Stretched PVA (polyvinyl alcohol) film and preparation method for same
CN103540049A (en) PVC (Polyvinyl Chloride) sythetic-wood ecologic furniture and partition panel and production method
CN103540050A (en) PVC (Polyvinyl Chloride) sythetic-wood ecologic indoor gate plate and production method thereof
CN102558781B (en) Glass fiber reinforced polyethylene glycol terephthalate (PET) engineering plastic material and manufacturing method of glass fiber reinforced PET engineering plastic material
CN102604347A (en) Preparation method of chitosan modified polylactic acid material by gamma-ray irradiation
WO2017167135A1 (en) Graphene microsheet master batch for enhancing bioplastic and preparation method thereof
CN107400493A (en) Degradable Adhesive composition and its production and use
CN107868417A (en) A kind of bagasse PLA composites suitable for 3D printing and its preparation method and application
CN106751616B (en) A kind of plasticizing polylactic acid material and preparation method thereof for 3D printing
CN110016213B (en) Polylactic acid foaming material with micro-nano composite pores and preparation method thereof
CN102558450B (en) Preparation method of high-melt-strength polypropylene
CN109280270B (en) Production method of high-temperature-resistant high-barrier polypropylene film
CN106810743A (en) PE and preparation method thereof is reclaimed in isomerism crosslinking toughness reinforcing enhancing
CN112430384B (en) Preparation process of bio-based degradable renewable energy polymeric plastic particles
CN106700209B (en) Composite foam material containing carbon nanofibers and preparation thereof
CN113427732B (en) Method for inducing formation of Shish-kebab precursor in polypropylene random copolymer by using waste IPP (interpenetrating polymer network) material
CN107602938A (en) A kind of preparation method of starch/EVA syntactic foam
CN107674278A (en) A kind of preparation method of NEW TYPE OF COMPOSITE Based Full-degradable Plastics Film

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17773165

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17773165

Country of ref document: EP

Kind code of ref document: A1