WO2003042294A1 - Procede de production d'une resine biodegradable - Google Patents

Procede de production d'une resine biodegradable Download PDF

Info

Publication number
WO2003042294A1
WO2003042294A1 PCT/CN2002/000271 CN0200271W WO03042294A1 WO 2003042294 A1 WO2003042294 A1 WO 2003042294A1 CN 0200271 W CN0200271 W CN 0200271W WO 03042294 A1 WO03042294 A1 WO 03042294A1
Authority
WO
WIPO (PCT)
Prior art keywords
starch
producing
biodegradable resin
resin according
dehydration
Prior art date
Application number
PCT/CN2002/000271
Other languages
English (en)
French (fr)
Inventor
Jiafan Liu
Shipu Quan
Original Assignee
Tianjin Danhai Co., Ltd.
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 Tianjin Danhai Co., Ltd. filed Critical Tianjin Danhai Co., Ltd.
Publication of WO2003042294A1 publication Critical patent/WO2003042294A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • 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

Definitions

  • the invention belongs to the technical field of resin preparation, and particularly relates to a method for producing a biodegradable resin.
  • plastic and non-woven fabric products are widely used in various fields of production and people's life, and their wastes are also increasing. Data show that the weight ratio of plastic and non-woven products in municipal solid waste has reached more than 10%, and the volume ratio has reached about 30%. Most of them are disposable packaging and daily-use miscellaneous goods. As ordinary plastics and non-woven materials are difficult to degrade and rot in the natural environment after use, the cost of manual collection and sorting is too high and difficult to promote, causing "white pollution", which has become a major issue for global environmental pollution control. At present, countries around the world have formulated strict policies and measures to reduce their environmental pollution. At the same time, they vigorously promote and support the research and development of degradable materials.
  • Degradable materials as high-tech products and environmentally friendly products, have become the research and development field of world attention today.
  • the development of this technology not only expands the functions of ordinary polymer materials, but also eases the contradiction between using ordinary polymer materials and protecting the environment, and the market prospect is very broad.
  • starch and resin composite biodegradable resin is an important research direction.
  • the molding material can be prepared from the master batch according to the traditional compounding and compounding method.
  • the molding material can be made into bags, bottles, foamed sheets, films, etc. using conventional molding techniques. Summary of the Invention
  • the invention adopts a new starch treatment technology to carry out liquid phase dehydration, multi-stage refinement and modification of starch, so that starch can be mixed with various resins.
  • the resin produced by this method has good quality and starch content as high as the biological Degraded 70% by weight of the resin.
  • the process can be continuously produced, the operation is easy to control, the product has no bubbles and water bubbles, and the product quality and biodegradability are excellent.
  • the invention aims to provide a production process and equipment for a biodegradable resin with good mixing of starch and resin, excellent biodegradability, continuous operation, 10,000-ton industrialization, and wide application range.
  • the main raw materials of this biodegradable resin include: thermoplastic resin, starch, liquid medium, coupling agent, lubricant, plasticizer and lowering agent.
  • thermoplastic resin is preferably: polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer, polyester or polyamide;
  • the starch is preferably: corn starch, wheat starch, potato starch, sweet potato starch or cassava starch Powder
  • the liquid medium is preferably: white oil, solvent oil;
  • the coupling agent is preferably a titanate coupling agent, an aluminate coupling agent, a silane coupling agent, or an aluminum-titanium composite coupling agent;
  • the lubricant is preferably: stearate, stearic acid, polyethylene wax or oxidized polyethylene; the plasticizer is preferably: dioctyl adipate, dioctyl sebacate or dioctyl phthalate;
  • the descending promoter is preferably: corn oil or epoxy soybean oil.
  • the production method of biodegradable resin includes starch drying, starch refinement, separation from liquid phase medium, starch modification and mixed granulation process.
  • the specific production process is:
  • the starch is dried using a dehydration kettle to make the water content of the starch less than 0.5%, preferably 0.2 to 0.5%; the starch and white oil or solvent oil are in a uniform weight ratio of 1: 1 to 2
  • the homogeneous sentence is mixed in the pulp kettle, and then the stirred starch slurry is put into a dehydration kettle for vacuum dehydration; the vacuum degree in the dehydration kettle is 0.050 to 0.095MPa, and the temperature is 100 to 160 ° C; of which solvent oil Solvent oil having a boiling point of 150 to 220 ° C at normal pressure is preferred.
  • the starch slurry is refined with a tandem sand mill to make the starch particle size smaller than 10 ⁇ m on average; starch particles with a particle size distribution of less than 10 ⁇ m account for 80% of the total starch weight the above.
  • the refined starch slurry is put into a separator such as a centrifuge, and the liquid phase medium is removed to obtain a starch filter cake;
  • the centrifuged starch cake is put into the mixer, preferably at a speed of 1300 to 1600 RPM High-speed mixer, adding 0.5-55% by weight of the dry starch coupling agent, 0.5-7.5% by weight of the dry starch to modify the lubricant; under the conditions of 1001 ⁇ 170 ° C, mixing 10 ⁇ Becomes modified starch after 50 minutes;
  • the above modified starch is added to a room temperature mixer with a thermoplastic resin with a dry starch weight of 25-80%, a plasticizer with a dry starch weight of 1-10%, and a dry starch weight of 0.5-7.5% lubricant and Mix 1 to 15% of the dry starch weight-lowering agent, mix and stir for 10-30 minutes before discharging;
  • twin-screw extruder or a kneading extruder with an aspect ratio of 40 to 48: 1 and an exhaust and mixing and plasticizing screw to extrude and granulate the mixture. It is preferably 100-290 ° C.
  • the method for producing a biodegradable resin wherein the starch is corn starch, wheat starch, potato starch, sweet potato starch or cassava starch.
  • the starch slurry after the dehydration and dehydration in the dehydration kettle is cooled to below 60 ° C in a cooling kettle.
  • the method for producing a biodegradable resin wherein the coupling agent is a titanate coupling agent, an aluminate coupling agent, a silane coupling agent, or an aluminum-titanium composite coupling agent.
  • the method for producing a biodegradable resin wherein the lubricant is stearate, stearic acid, polyethylene wax or oxidized polyethylene.
  • thermoplastic resin is polyethylene, polypropylene, polyethylene, ethylene-vinyl acetate copolymer, polyester or polyamide.
  • thermoplastic resin is polyethylene, and is selected from high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), a mixture of HDPE and LLDPE, or A mixture of LDPE and LLDPE.
  • the plasticizer is: dioctyl adipate, dioctyl sebacate or dioctyl o-formate.
  • the descending promoter is corn oil or epoxy soybean oil.
  • the starch sanding is continuously performed by using 3 to 7 sand mills in series.
  • the extrusion granulation process has two-stage exhaust.
  • Two-stage exhaust can reduce the volatile content in the product, and avoid bubbles and water bubbles during the production of products, especially membrane products and fiber products.
  • the granulation is performed by hot air cooling or pull bar.
  • the starch dehydration technology used in the present invention can reduce the moisture content of starch to 0.5% or less.
  • the continuous miniaturization technology can be used to make the average starch particle size ⁇ 10 ⁇ m and the particle size uniform, which increases the surface area of the starch and ensures the quality of its downstream products.
  • biodegradable resin has good degradation performance, but also can save limited petroleum resources and greatly reduce the amount of polymer material waste generated.
  • the biodegradable resin has good degradation performance, but also can save limited petroleum resources and greatly reduce the amount of polymer material waste generated.
  • due to the addition of a large amount of starch and a descending agent its waste is conducive to composting, which is a unique way of recycling, which is in line with recyclable treatment measures.
  • Biodegradable resin can be widely used in the production of disposable packaging materials, agricultural mulch, Non-woven fabrics, injection blow molded products, sheet products, foamed materials, seedling bowls, etc.
  • biodegradable resin can be widely used in the production of disposable packaging materials, agricultural mulch, Non-woven fabrics, injection blow molded products, sheet products, foamed materials, seedling bowls, etc.
  • 1500 Kg of industrial corn starch and solvent oil (boiling point is 155 ° C under normal pressure) are mixed in a homogenizer at a weight ratio of 1: 1.5, and then the homogenized starch slurry is put into a dehydration tank for vacuum dehydration;
  • the vacuum in the dehydration kettle is 0.08 MPa, the temperature is 120 ° C, and the water content in the starch is dried to 0.35%.
  • the starch slurry was then cooled to 56 in a cooling kettle.
  • the starch slurry was refined with 4 sand mills connected in series, so that the starch particle size was reduced to an average of 7.9 ⁇ m, and 85% of the starch particle size was below 10 ⁇ m.
  • the refined starch slurry was put into a centrifuge, and the liquid phase medium was removed to obtain a starch filter cake.
  • the starch filter cake was put into the high-speed mixer for several times, each time 150 kg of starch filter cake was added, and 1.5 Kg of titanate coupling agent LICA38 and 1.5 Kg of lubricant stearic acid were added for modification; at 110 ° C Under the conditions, it will become modified starch after mixing for 20 minutes;
  • the above modified starch was added to a room temperature mixer, with 75Kg of thermoplastic resin high-density polyethylene, 1.5Kg of plasticizer dioctyl phthalate, 1.5Kg of lubricant stearic acid, and 3 Kg of epoxy soybean oil Mix, mix and stir for 20 minutes before discharging;
  • Example 2 The above-mentioned mixture is extruded and granulated into a biodegradable resin by a mixing extruder, and the extrusion granulation process temperature is 170-190 ° C. The granulating head is eagerly air-cooled. Through the above steps, a biodegradable resin with excellent properties is obtained.
  • Example 2 The above-mentioned mixture is extruded and granulated into a biodegradable resin by a mixing extruder, and the extrusion granulation process temperature is 170-190 ° C. The granulating head is eagerly air-cooled. Through the above steps, a biodegradable resin with excellent properties is obtained.
  • Example 2 Example 2
  • the starch slurry was refined by 5 sand mills connected in series, so that the particle size of the starch was reduced to an average of 7.4 ⁇ m, and 89% of the starch particle size was below 10 ⁇ m. %.
  • the refined starch slurry was put into a centrifuge, and the liquid phase medium was removed to obtain a starch filter cake.
  • the starch filter cake was divided into high-speed mixers, and 150 kg of starch filter cake was added each time, and 3 Kg of aluminate coupling agent DL-411 and 6 Kg of lubricant polyethylene ⁇ were added for modification. Under the condition of ° C, it will become modified starch after mixing for 28 minutes;
  • the mixture was extruded and granulated into a biodegradable resin using a twin-screw extruder with a length-to-diameter ratio of 44: 1 and a two-stage exhaust and mixing and plasticizing screw.
  • the extrusion granulation process temperature was 200-2301: .
  • the granulating head is eagerly air-cooled. Through the above steps, a biodegradable resin with excellent performance is obtained.
  • the wheat starch 1500 Kg and industrial white oil are mixed uniformly in a homogenizer according to a weight ratio of 1: 2, and then the starch slurry of the stirrer is put into a dehydration kettle for vacuum dehydration; the vacuum degree in the dehydration kettle is 0.07MPa 3% ⁇ , the temperature was 130 ° C, dried to a starch water content of 0.3%.
  • the starch slurry was then placed in a cooling kettle and cooled to 55 ° C.
  • the cooled starch slurry is refined by 3 sand mills connected in series.
  • the particle size of the starch was refined to an average of 8.2 ⁇ m, and 83% of the starch particles had a particle size of 10 ⁇ m or less.
  • the refined starch slurry was put into a centrifuge, and the liquid phase medium was removed to obtain a starch filter cake.
  • the starch filter cake was divided into high-temperature and high-speed mixers, and 150 kg of starch filter cake was added each time.
  • 1.2 Kg aluminum-titanium composite coupling agent 0L-AT1618 and 2 Kg lubricant magnesium stearate were added for modification. ; At 160 ° C, after mixing for 22 minutes, it becomes modified starch;
  • the above modified starch was added to a room temperature mixer and mixed with 75 kg of a thermoplastic resin ethylene-vinyl acetate copolymer, 3 Kg of a plasticizer dioctyl sebacate, 2 Kg of a lubricant magnesium stearate, and 3 Kg of a corn oil lowering agent. , Mix and stir for 22 minutes before discharging;
  • the above mixture was extruded and granulated into a biodegradable resin with a twin-screw extruder with an aspect ratio of 40: 1 and a two-stage exhaust and mixing and plasticizing screw.
  • the extrusion granulation process temperature was 150 ⁇ 160 ° C.
  • the granulating head is eagerly air-cooled. Through the above steps, a biodegradable resin with excellent performance is obtained.
  • the starch slurry was refined by 7 sand mills connected in series, so that the particle size of the starch was reduced to an average of 5.4 ⁇ m, and the particle size of the starch particles below 10 ⁇ m accounted for 92. %.
  • the refined starch slurry was put into a centrifuge, and the liquid phase medium was removed to obtain a starch filter cake.
  • the starch filter cake is put into the high-temperature high-speed mixer for several times, each time it is put into 150 Kilogram starch filter cake, adding titanate coupling agent KR TTS 4Kg, lubricant polyethylene wax 3kg for modification; at 140 ° C, mixing for 30 minutes to become modified starch;
  • thermoplastic resin polyester 45 Kg plasticizer dioctyl phthalate 7.5 Kg, lubricant polyethylene wax 3 Kg, drop-down promoting agent epoxy soybean oil 4 . 5Kg mixing, mixing and stirring for 30 minutes before discharging;
  • the mixture was extruded and granulated into a biodegradable resin with a twin-screw extruder with a length-to-diameter ratio of 48: 1 and a two-stage exhaust and mixing and plasticizing screw.
  • the temperature of the extrusion granulation process was 270-290 °. C.
  • the granulating head is eagerly air-cooled.
  • the starch is cassava starch
  • the coupling agent for starch modification is silane coupling agent KH570
  • the modification temperature is 150 * C
  • the thermoplastic resin is polypropylene
  • the extruder adopts an aspect ratio of 48: 1 with two-stage row A twin-screw extruder for gas and mixing plasticized screw pestle.
  • the extrusion granulation head is a pull bar type.
  • the granulation temperature is 150 ⁇ 170 ° C.
  • Other conditions are the same as in Example 1. A biodegradation with excellent performance is obtained. Resin performance is excellent.
  • the lubricant used is oxidized polyethylene
  • the thermoplastic resin is polyamide
  • the pelletizing head is a draw bar type
  • the extrusion granulation temperature is 230-280 ° C

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Description

生物降解树脂的生产方法 技术领域
本发明属于树脂制备技术领域，特别是涉及一种生物降解树脂 的生产方法。
背景技术
随着高分子材料工业技术的迅速发展， 在塑料和非织造布制品 广泛应用于生产和人民生活的各个领域的同时， 其废弃物也日益增 多。 有资料显示， 城市固体废弃物中塑料及非织造布制品的重量比 已达 10%以上， 体积比已达 30%左右， 其中大部分为一次性包装物和 日用杂品。 由于普通塑料及非织造布材料使用后在自然环境中难于 降解、 腐烂， 人工收集与分捡的成本过高， 难于推广， 造成了 "白 色污染"， 成为全球性环境污染治理的重大课题。 目前， 世界各国均 制订了严格的政策措施以减少其对环境的污染， 同时大力提倡并支 持可降解材料的研究与开发。
降解材料作为高科技产品和环保产品， 已经成为当今世界瞩目 的研究开发领域。 这项技术的发展不但扩展了普通高分子材料的功 能， 而且緩解了使用普通高分子材料与保护环境的矛盾， 市场前景 十分广阔。 其中淀粉与树脂复合的生物降解树脂是一个重要的研究 方向。
当前， 对淀粉进行脱水、 细化处理的报道不多， 所见的有 W095/04082 "Heat treated noncohesive starches and flours and process for their production" (热处理的非粘性淀粉和谷粉及 其制备方法）， 报道了采用流化床对淀粉进行脱水，脱水后淀粉含水 量小于 5wt%; US 5929231 "Method for preparing fine-granuled and modified starches " (细化和改性淀粉的制备方法）， 所用原 料为燕麦和大米， 通过辊的研磨细化， 使原来粒径在 5 ~ 10 μ πι的燕 麦或大米淀粉细化至平均粒径为 3 ~ 5 μ πι ; US 5667574 "Starch— based composition for preparing an environment degradable alpha— olefinic polymer molding materal" (用于制 备可环境降解 α -烯烃聚合物模塑材料的淀粉基组合物）， 其中叙述 了一种母料的制备方法， 包括： 将 95- 99 (重量）份淀粉、 0. 2-0. 8 份钛酸酯偶联剂、 0-2 份石蜡、 0-2份脂肪酸混合； 所得的混合物 50-80份与 18-49. 8份 a -烯烃聚合物、 0. 1-1. 0份光敏剂、 0. 1-1. 0 份光敏促进剂在 120-10°C下搅拌 5-10分钟， 所得熔融混合物冷却、 造粒即得此母料，模塑材料可由此母料按传统配混复合方法制得，可 使用传统的模塑技术， 将此模塑材料制成袋、 瓶、 发泡片材、 膜等。 发明内容
本发明采用一种新的淀粉处理技术对淀粉进行液相脱水、 多级 细化和改性， 使淀粉能与多种树脂混熔， 用此方法生产的树脂质量 好、淀粉含量可高达该生物降解树脂重量的 70%。本工艺可连续生产， 操作易控制， 产品无气泡、 水泡， 产品质量和生物降解性能优良。
本发明旨在提供一种淀粉与树脂混熔良好、生物降解性能优良、 连续运转的、 万吨级产业化的、 应用范围广的生物降解树脂的生产 工艺及设备。
本生物降解树脂的主要原料包括： 热塑性树脂、 淀粉、 液相介 质、 偶联剂、 润滑剂、 增塑剂和促降剂等。
其中：
热塑性树脂优选为：聚乙烯、 聚丙烯、 聚苯乙烯、 乙烯-醋酸乙 烯共聚物、 聚酯或聚酰胺；
淀粉优选为：玉米淀粉、 小麦淀粉、 土豆淀粉、 红薯淀粉或木薯淀 粉；
液相介质优选为：白油、 溶剂油；
偶联剂优选为：钛酸酯偶联剂、铝酸酯偶联剂、硅烷偶联剂或铝钛 复合偶联剂；
润滑剂优选为： 硬脂酸盐、 硬脂酸、 聚乙烯蜡或氧化聚乙烯； 增塑剂优选为： 己二酸二辛酯、 癸二酸二辛酯或邻苯二甲酸二辛酯； 促降剂优选为： 玉米油或环氧大豆油。
本发明采用如下技术方案：
生物降解树脂的生产方法， 包括淀粉干燥、 淀粉细化、 与液相 介质分离、 淀粉改性和混合造粒工艺过程， 其具体的生产工艺过程 为：
(1) 淀粉干燥
淀粉干燥采用脱水釜脱水方式， 使淀粉中的水含量低于 0. 5%, 优选 0. 2-0. 5%;将淀粉和白油或溶剂油按 1 : 1 ~ 2的重量比在均浆釜 中混合均句， 然后将搅勾的淀粉浆料放入脱水釜中进行真空脱水； 脱水釜中的真空度为 0. 050 ~ 0. 095MPa, 温度为 100 - 160°C ; 其中 溶剂油优选为常压下沸点为 150 - 220°C的溶剂油。
(2)淀粉细化
冷却后的淀粉浆料采用串联砂磨机组进行细化处理， 使淀粉的 粒径细化至平均 ΙΟ μ πι以下； 优选粒径分布为小于 ΙΟ μ πι的淀粉颗 粒占淀粉总重量的 80%以上。
(3)脱去液相介质
细化后的淀粉浆料放入例如离心机的分离器中， 脱去其中的液 相介质， 得到淀粉滤饼；
(4)淀粉改性
离心后的淀粉滤饼投入混合机中， 优选转速为 1300至 1600RPM 的高速混合机， 加入干燥淀粉重量 0. 5-5 %的偶联剂、 干燥淀粉重 量 0. 5-7. 5 %的润滑剂进行改性；在1001 ~ 170 °C条件下，混合 10 ~ 50分钟后成为变性淀粉；
(5)与热塑性树脂混合
将上述变性淀粉加入到室温混合机中，与干燥淀粉重量 25-80% 的热塑性树脂、 干燥淀粉重量 1-10%的增塑剂、 干燥淀粉重量 0. 5- 7. 5 %的润滑剂和干燥淀粉重量 1-15%的促降剂混合， 混合搅拌 10 - 30分钟后出料；
(6)挤出造粒
优选用长径比为 40 ~ 48 : 1 并带有排气及混炼塑化螺杆的双螺 杆挤出机或混炼式挤出机将上述混合料挤出造粒， 挤出造粒工艺温 度优选为 100- 290°C。
本发明还可以采用如下优选实施方案：
所述的生物降解树脂的生产方法， 其中淀粉为玉米淀粉、 小麦 淀粉、 土豆淀粉、 红薯淀粉或木薯淀粉。
所述的生物降解树脂的生产方法， 其中脱水釜脱水干燥后的淀 粉浆料要在冷却釜中冷却至 60°C以下。
所述的生物降解树脂的生产方法， 其中偶联剂为钛酸酯偶联剂、 铝酸酯偶联剂、 硅烷偶联剂或铝钛复合偶联剂。
所述的生物降解树脂的生产方法， 其中润滑剂为硬脂酸盐、 硬 脂酸、 聚乙烯蜡或氧化聚乙烯。
所述的生物降解树脂的生产方法， 其中热塑性树脂为聚乙烯、 聚丙烯、 聚笨乙烯、 乙烯-醋酸乙烯共聚物、 聚酯或聚酰胺。
所述的生物降解树脂的生产方法， 其中热塑性树脂为聚乙烯， 选自高密度聚乙烯（HDPE )、 低密度聚乙烯（LDPE)、 线性低密度聚乙 烯（LLDPE)、 HDPE和 LLDPE的混合物或 LDPE和 LLDPE的混合物。 所述的生物降解树脂的生产方法，其中增塑剂为： 己二酸二辛酯， 癸二酸二辛酯或邻 甲酸二辛酯。
所述的生物降解树脂的生产方法，其中促降剂为玉米油或环氧大 豆油。
所述的生物降解树脂的生产方法， 其中淀粉砂磨细化采用 3 - 7 台砂磨机串联方式连续进行。
所述的生物降解树脂的生产方法， 其中挤出造粒过程有两级排 气。 两级排气可減少产品中的挥发物含量， 避免制品特别是膜制品 及纤维制品生产时产生气泡、 水泡。 造粒采用热切风冷或拉条式进 行。
本发明具有的优点和积极效果：
( 1 )本发明采用的淀粉脱水技术， 可将淀粉的水分降到 0. 5% 以下。
( 2 )采用连续式的微细化处理技术， 可使淀粉平均粒径 < 10 μ πι, 并且颗粒粒度均匀， 增大了淀粉的表面积， 保证了其下游制品 的质量。
( 3 )加入多种改性剂， 对淀粉进行覆羟改性， 降低了淀粉的 表面亲水性， 提高了淀粉在基料中的分散性和与基体树脂的相容性, 提高了淀粉在树脂和制品中的含量。
( 4 )采用大长径比、 特殊螺杆组合、 带有排气及混炼塑化螺 杆的造粒设备， 确保了树脂的质量。
这不仅意味着生物降解树脂具有良好的降解性能， 而且可以节 约有限的石油资源， 大大减少高分子材料垃圾的产生量。 另外， 由 于加入了大量淀粉和促降剂， 其废弃物有利于堆肥化处理， 是回收 利用的一种独特方式， 符合再资源化的治理措施。
生物降解树脂可广泛应用于生产一次性包装材料、 农用地膜、 非织造布、 注吹塑制品、 片材制品、 发泡材料、 育苗钵等。 为能进一步了解本发明的技术内容、 特点及功效， 兹列举以下 实例， 详细说明如下：
实施例 1
将工业玉米淀粉 1500 Kg和溶剂油（常压下沸点为 155°C )按 1:1.5重量比在均浆釜中混合均匀，然后将搅匀的淀粉浆料放入脱水 釜中进行真空脱水； 脱水釜中的真空度为 0.08MPa, 温度为 120°C, 干燥至淀粉中的水含量为 0.35%。然后将淀粉浆料放入冷却釜中冷却 至 56 。
冷却后的淀粉浆料采用 4 台串联的砂磨机组对其进行细化处 理， 使淀粉的粒径细化至平均 7.9μιη， 并且淀粉颗粒粒径在 10 μπι 以下的占 85%。
细化后的淀粉浆料放入离心机， 脱去其中的液相介质， 得到淀 粉滤饼。
离心后的淀粉滤饼分多次投入高速混合机中， 每次投入 150公 斤淀粉滤饼， 加入 1.5 Kg钛酸酯偶联剂 LICA38、 1.5 Kg润滑剂硬 脂酸进行改性； 在 110°C条件下， 混合 20分钟后成为变性淀粉；
将上述变性淀粉加入到室温混合机中， 与热塑性树脂高密度聚 乙烯 75Kg、 增塑剂邻苯二甲酸二辛酯 1.5 Kg、 润滑剂硬脂酸 1.5Kg、 促降剂环氧大豆油 3 Kg混合， 混合搅拌 20分钟后出料；
用混炼式挤出机将上述混合料挤出造粒成生物降解树脂， 挤出 造粒工艺温度为 170~190 。 造粒机头为热切风冷式。 经过以上工 序， 制得性能优良的生物降解树脂。 实施例 2
将工业土豆淀粉 1500 Kg和工业白油按 1 : 1. 8重量比在均浆釜 中混合均勾， 然后将搅勾的淀粉浆料放入脱水釜中进行真空脱水； 脱水釜中的真空度为 0. 06MPa， 温度为 140°C , 干燥至淀粉中的水含 量为 0. 45%。 然后将淀粉浆料放入冷却釜中冷却至 50°C。
冷却后的淀粉浆料采用 5 台串联的砂磨机组对其进行细化处 理， 使淀粉的粒径细化至平均 7. 4 μ πι, 并且淀粉颗粒粒径在 10 μ πι 以下的占 89%。
细化后的淀粉浆料放入离心机， 脱去其中的液相介质， 得到淀 粉滤饼。
离心后的淀粉滤饼分多次投入高速混合机中， 每次投入 150公 斤淀粉滤饼， 加入 3 Kg铝酸酯偶联剂 DL- 411、 6 Kg润滑剂聚乙烯 蟠进行改性； 在 120°C条件下， 混合 28分钟后成为变性淀粉；
-将上述变性淀粉加入到室温混合机中， 与热塑性树脂聚苯乙烯 60 Kg、 增塑剂己二酸二辛酯 4. 5 Kg、 润滑剂聚乙烯蜡 8 Kg. 促降 剂玉米油 6 Kg混合， 混合搅拌 12分钟后出料；
用长径比为 44: 1 带有两级排气及混炼塑化螺杆的双螺杆挤出 机将上述混合料挤出造粒成生物降解树脂， 挤出造粒工艺温度为 200 - 2301：。 造粒机头为热切风冷式。 经过以上工序， 制得性能优 良的生物降解树脂。
实施例 3
将小麦淀粉 1500 Kg和工业白油按 1 :2重量比在均浆釜中混合均 匀， 然后将搅勾的淀粉浆料放入脱水釜中进行真空脱水； 脱水釜中 的真空度为 0. 07MPa,温度为 130°C ,干燥至淀粉中的水含量为 0. 3%。 然后将淀粉浆料放入冷却釜中冷却至 55°C；。
冷却后的淀粉浆料采用 3 台串联的砂磨机组对其进行细化处 理， 使淀粉的粒径细化至平均 8. 2 μ πι, 并且淀粉颗粒粒径在 10 μ πι 以下的占 83%。
细化后的淀粉浆料放入离心机， 脱去其中的液相介质， 得到淀 粉滤饼。
离心后的淀粉滤饼分多次投入高温高速混合机中，每次投入 150 公斤淀粉滤饼， 加入 1. 2 Kg铝钛复合偶联剂 0L-AT1618、 2Kg润滑 剂硬脂酸镁进行改性； 在 160 °C条件下， 混合 22分钟后成为变性淀 粉；
将上述变性淀粉加入到室温混合机中， 与热塑性树脂乙烯-醋酸 乙烯共聚物 75Kg、 增塑剂癸二酸二辛酯 3 Kg、 润滑剂硬脂酸镁 2 Kg、 促降剂玉米油 3Kg混合， 混合搅拌 22分钟后出料；
用长径比为 40: 1 带有两级排气及混炼塑化螺杆的双螺杆挤出 机将上述混合料挤出造粒成生物降解树脂， 挤出造粒工艺温度为 150 ~ 160°C。 造粒机头为热切风冷式。 经过以上工序， 制得性能优 良的生物降解树脂。
实施例 4
将红薯淀粉 1500 Kg和工业白油按 1 : 1. 2重量比在均浆釜中混 合均勾， 然后将搅勾的淀粉浆料放入脱水釜中进行真空脱水； 脱水 釜中的真空度为 0. 095MPa， 温度为 160°C， 干燥至淀粉中的水含量 为 0. 25%。 然后将淀粉浆料放入冷却釜中冷却至 58°C。
冷却后的淀粉浆料采用 7 台串联的砂磨机组对其进行细化处 理， 使淀粉的粒径细化至平均 5. 4 μ πι， 并且淀粉颗粒粒径在 10 μ πι 以下的占 92%。
细化后的淀粉浆料放入离心机， 脱去其中的液相介质， 得到淀 粉滤饼。
离心后的淀粉滤饼分多次投入高温高速混合机中，每次投入 150 公斤淀粉滤饼， 加入钛酸酯偶联剂 KR TTS 4Kg、 润滑剂聚乙烯蜡 3kg 进行改性； 在 140°C条件下， 混合 30分钟后成为变性淀粉；
将上述变性淀粉加入到室温混合机中， 与热塑性树脂聚酯 45 Kg、 增塑剂邻苯二甲酸二辛酯 7. 5 Kg、 润滑剂聚乙烯蜡 3 Kg、 促降剂 环氧大豆油 4. 5Kg混合， 混合搅拌 30分钟后出料；
用长径比为 48 : 1 带有两级排气及混炼塑化螺杆的双螺杆挤出 机将上述混合料挤出造粒成生物降解树脂， 挤出造粒工艺温度为 270-290°C。 造粒机头为热切风冷式。 经过以上工序， 制得性能优良 的生物降解树脂。
实施例 5
除了淀粉为木薯淀粉， 淀粉改性用偶联剂为硅烷偶联剂 KH570， 改性温度为 150*C , 热塑性树脂采用聚丙烯， 挤出机采用长径比为 48 : 1带有两级排气及混炼塑化螺杵的双螺杆挤出机， 挤出造粒机头 为拉条式， 造粒温度为 150 ~ 170°C， 其他条件同实施例 1, 制得性 能优良的生物降解树脂性能优良。
实施例 6
除了淀粉改性和与热塑性树脂混合步骤中采用的润滑剂都为氧 化聚乙烯， 热塑性树脂采用聚酰胺， 造粒机头为拉条式， 挤出造粒 温度为 230-280°C , 其他条件同实施例 2, 制得性能优良的生物降解 树脂。

Claims

权 利 要 求
1. 生物降解树脂的生产方法， 包括以下步糠：
(1) 采用脱水釜脱水方式将淀粉和白油或溶剂油在均浆釜中混 合均匀， 真空脱水使淀粉中的水含量低于 0.5%;
(2) 冷却后的淀粉浆料细化至淀粉平均粒径 ΙΟμπι以下；
(3)脱去细化后的淀粉浆料中的液相介质， 得到淀粉滤饼；
(4)将所得淀粉滤饼在混合机中与干燥淀粉重量 0，5- 5% 的偶 联剂、 干燥淀粉重量 0.5-7.5 %的润滑剂混合以进行改性；
(5) 将上述变性淀粉加入到室温混合机中，与干燥淀粉重量 25 - 80%的热塑性树脂、 干燥淀粉重量 1-10%的增塑剂、 干燥淀粉重 量 0.5- 7.5%的润滑剂和干燥淀粉重量 1-15 %的促降剂混合；
(6)将上述得到的混合物挤出造粒。
2. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 淀 粉干燥过程是将淀粉和白油或溶剂油按 1： 1 ~ 2重量比例在均浆釜中 混合均匀， 然后将搅勾的淀粉浆料放入脱水釜中进行真空脱水， 脱 水釜中的真空度为 0.05 0.095MPa, 温度为 100~160。C。
3. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 淀 粉细化过程是采用串联砂磨机组进行细化处理。
4. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 淀粉改 性的工艺温度为 100°C - 170°C, 混合时间为 10~ 50分钟。
5. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 与 热塑性树脂混合搅拌时间为 10~ 30分钟。
6. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 用 有混炼塑化螺杆的双螺杆挤出机或混炼式挤出机将上述混合料挤出 造粒。
7. 根据权利要求 6所述的生物降解树脂的生产方法， 其中： 所 述双螺杆挤出机的螺杆长径比为 40 - 48 : 1并带有排气功能，挤出造 粒温度为 100 ~ 290°C。
8. 根据权利要求 1所迷的生物降解树脂的生产方法， 其中： 淀 粉为玉米淀粉、 小麦淀粉、 土豆淀粉、 红薯淀粉或木薯淀粉。
9. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 脱 水釜脱水干燥后的淀粉浆料要在冷却釜中冷却至 60°C以下。
10. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 偶 联剂为钛酸酯偶联剂、 铝酸酯偶联剂、 硅烷偶联剂或铝钛复合偶联 剂。
11. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 润 滑剂为硬脂酸盐、 硬脂酸、 聚乙烯蜡或氧化聚乙烯。
12. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 热 塑性树脂为聚乙烯、 聚丙烯、 聚苯乙烯、 乙烯 -醋酸乙烯共聚物、 聚. 酯或聚酰胺。
13. 根据权利要求 1所迷的生物降解树脂的生产方法， 其中： 增 塑剂为己二酸二辛酯、 务二酸二辛酯或邻 甲酸二辛酯。
14. 根据权利要求 1所述的生物降解树脂的生产方法， 其中： 促 降剂为玉米油或环氧大豆油。
15. 根据权利要求 3所述的生物降解树脂的生产方法， 其中： 淀 粉砂磨细化采用 3 ~ 7台砂磨机串联方式连续进行。
16. 根据权利要求 7所述的生物降解树脂的生产方法， 其中： 挤 出造粒过程有两级排气， 造粒采用热切风冷或拉条式进行。
17. 根据权利要求 12所述的生物降解树脂的生产方法， 其中： 热 塑性树脂聚乙烯选自高密度聚乙烯、 低密度聚乙烯、 线性低密度聚 乙烯、 高密度聚乙烯和线性低密度聚乙烯的混合物或低密度聚乙烯 和线性低密度聚乙烯的混合物
PCT/CN2002/000271 2001-11-15 2002-04-19 Procede de production d'une resine biodegradable WO2003042294A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN01134820.8 2001-11-15
CN01134820A CN1363625A (zh) 2001-11-15 2001-11-15 生物降解树脂的生产方法

Publications (1)

Publication Number Publication Date
WO2003042294A1 true WO2003042294A1 (fr) 2003-05-22

Family

ID=4672770

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2002/000271 WO2003042294A1 (fr) 2001-11-15 2002-04-19 Procede de production d'une resine biodegradable

Country Status (4)

Country Link
US (1) US20030092793A1 (zh)
JP (1) JP2003145534A (zh)
CN (1) CN1363625A (zh)
WO (1) WO2003042294A1 (zh)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7402618B2 (en) * 2000-11-23 2008-07-22 Hao Xu Biodegradable composition for the preparation of tableware, drink container, mulching film and package and method for preparing the same
CN1121452C (zh) * 2000-11-23 2003-09-17 许浩 生物降解环保型餐具的配方及生产工艺
CN100376626C (zh) * 2002-08-28 2008-03-26 周维文 一种香味抗菌降解聚烯烃组合物及其制造方法及用途
CN1230466C (zh) * 2003-02-25 2005-12-07 丁少忠 一种可完全生物降解塑料母料及其制备方法
DE10336387A1 (de) * 2003-08-06 2005-03-03 Basf Ag Biologisch abbaubare Polyestermischung
FR2871166B1 (fr) * 2004-06-04 2006-12-01 Creca Sa Composition thermoplastique biodegradable et procede de preparation
DE102007050770A1 (de) * 2007-10-22 2009-04-23 Biotec Biologische Naturverpackungen Gmbh & Co. Kg Polymeres Material und Verfahren zu dessen Herstellung
DE102007050769A1 (de) 2007-10-22 2009-04-23 Biotec Biologische Naturverpackungen Gmbh & Co. Kg Polymeres Material und Verfahren zu dessen Herstellung
EP2307495B1 (en) * 2008-07-31 2016-10-12 Tristano Pty Ltd Compositions comprising thermoplastic starch
US20100230405A1 (en) * 2009-03-11 2010-09-16 Nuvision Bioplastics, Llc Biodegradable Resin Composition Utilized in the Manufacture of Biodegradable Containers, Biodegradable Containers, and Method of Manufacture
CN102504347B (zh) * 2011-11-16 2014-12-10 和昌（广西）化工有限公司 可降解聚烯烃母粒及生产方法
US20140274682A1 (en) * 2013-03-15 2014-09-18 Bayer Cropscience Lp Compositions and methods for reducing dust and repelling, controlling, or directing an insect
CN103351483B (zh) * 2013-07-24 2016-05-11 济南大学 微球型高疏水性淀粉及其制备方法及应用
CN104756789A (zh) * 2015-04-03 2015-07-08 南京工业大学 一种含矿物的育苗盘及其制备方法
CN108586819A (zh) * 2018-05-03 2018-09-28 韩毅忠 一种可降解淀粉基材料
CN108795001B (zh) * 2018-05-28 2020-04-07 金发科技股份有限公司 一种可生物降解聚合物组合物及其应用
CN111057356B (zh) * 2019-12-23 2021-11-12 江苏郁林生塑木科技有限公司 一种聚乳酸基生物质复合材料板材及其制备方法
CN111410827A (zh) * 2020-04-13 2020-07-14 荆门市诺维英新材料科技有限公司 一种可降解医用薄膜材料及其制备方法
CN112375344B (zh) * 2020-10-21 2023-02-17 浙江华发生态科技有限公司 一种全生物降解吹膜材料及加工工艺
CN112457534A (zh) * 2020-11-19 2021-03-09 杭州金焱包装彩印有限公司 用于食品包装材料的生物降解热塑性淀粉树脂及其制备方法
CN113754990A (zh) * 2021-08-26 2021-12-07 江苏诚盟装备股份有限公司 一种淀粉基全生物降解材料及其制备方法
CN114634769B (zh) * 2022-03-18 2023-07-14 揭阳市国为新技术有限公司 一种可降解模内贴标及其制备方法和可降解塑料瓶的处理方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1232834A (zh) * 1999-02-11 1999-10-27 天津丹海股份有限公司 生物降解塑料母料的制备方法
CN1280146A (zh) * 2000-07-13 2001-01-17 天津丹海股份有限公司 可生物降解纤维级树脂组合物及其生产方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH671961A5 (zh) * 1987-02-27 1989-10-13 Amrotex Ag
US5216043A (en) * 1991-12-12 1993-06-01 Minnesota Mining And Manufacturing Company Degradable thermophastic compositions and blends with naturally biodegradable polymers
US5703160A (en) * 1992-07-15 1997-12-30 Solvay S.A. Biodegradable moulding compositions comprising a starch, a biodegradable polyester, and a salt of a hydroxycarboxylic acid
FI96317C (fi) * 1994-05-31 1996-06-10 Exavena Oy Menetelmä hienojakoisten ja muunnettujen tärkkelyksien valmistamiseksi
US5667574A (en) * 1996-11-06 1997-09-16 Chi May Co., Ltd. Starch-based composition for preparing an environment degradable α-olefinic polymer molding material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1232834A (zh) * 1999-02-11 1999-10-27 天津丹海股份有限公司 生物降解塑料母料的制备方法
CN1280146A (zh) * 2000-07-13 2001-01-17 天津丹海股份有限公司 可生物降解纤维级树脂组合物及其生产方法

Also Published As

Publication number Publication date
JP2003145534A (ja) 2003-05-20
CN1363625A (zh) 2002-08-14
US20030092793A1 (en) 2003-05-15

Similar Documents

Publication Publication Date Title
WO2003042294A1 (fr) Procede de production d&#39;une resine biodegradable
CN110791069B (zh) 一种软包装用全降解高阻隔复合材料
CN1315919C (zh) 具有改进物理性能的聚乙烯薄膜
CN102108196B (zh) 一种聚乳酸可降解材料的制备方法
CN113801350A (zh) 一种碳酸钙填充pbat/pla生物降解塑料薄膜及其制备方法
CN1228101A (zh) 具有改进的隔离性能的高密度聚乙烯薄膜
WO2002042378A1 (fr) Composition biodegradable pour la preparation d&#39;articles de table, film de paillage et emballage, et leur procede de preparation
CN101591467A (zh) 一种聚乳酸基木/塑复合材料及其制备方法
CN111410822B (zh) 一种pbat/pla淀粉基完全生物降解材料及其制备方法
CN113416362A (zh) 一种利用废旧塑料制备再生塑料的方法
CN112210196A (zh) 一种可生物降解聚乳酸制品及其制备方法
CN1786072A (zh) 多元组合可降解发泡塑料及其制备方法
CN100494236C (zh) 一种改性淀粉的制备方法
CN104403198A (zh) 一种硅酸钙/聚烯烃复合材料的制备方法
CN100592979C (zh) 聚烯烃全透明母粒及其制备方法
CN1951994A (zh) 透明薄膜母料及其制备方法
CN113354928B (zh) 一种用于制作降解膜的生物塑料及制备方法
CN114921069B (zh) 一种高热封强度的全生物降解薄膜及其制备方法和应用
CN114589831B (zh) 原位反应挤出塑化或塑化增容工艺制备热塑性淀粉或淀粉/高分子共混物
CN114045010A (zh) 一种生物降解聚酯薄膜及其制备方法
CN103214722A (zh) 一种易与植物碎料均混的聚烯烃粉末及其制备方法
CN1232834A (zh) 生物降解塑料母料的制备方法
CN112390999A (zh) 一种hdpe再生料、其制备方法及hdpe管材
CN101376726A (zh) 具有自润滑作用的可生物降解塑料电子钟壳及其制备方法
CN108794816A (zh) 一种生物质热塑复合材料及其制备方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase