WO2019080524A1 - 一种聚乳酸复合材料及其应用 - Google Patents

一种聚乳酸复合材料及其应用

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Publication number
WO2019080524A1
WO2019080524A1 PCT/CN2018/092804 CN2018092804W WO2019080524A1 WO 2019080524 A1 WO2019080524 A1 WO 2019080524A1 CN 2018092804 W CN2018092804 W CN 2018092804W WO 2019080524 A1 WO2019080524 A1 WO 2019080524A1
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Prior art keywords
polylactic acid
acid composite
composite material
mfi
weight
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2018/092804
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English (en)
French (fr)
Inventor
卢昌利
袁志敏
蔡彤旻
黄险波
曾祥斌
焦建
熊凯
杨晖
麦开锦
董学腾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials Co Ltd
Original Assignee
ZHUHAI WANGO CHEMICAL CO Ltd
Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
Tianjin Kingfa Advanced Materials 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 ZHUHAI WANGO CHEMICAL CO Ltd, Kingfa Science and Technology Co Ltd, Shanghai Kingfa Science and Technology Co Ltd, Tianjin Kingfa Advanced Materials Co Ltd filed Critical ZHUHAI WANGO CHEMICAL CO Ltd
Priority to EP18870964.6A priority Critical patent/EP3666826B1/en
Priority to KR1020207006982A priority patent/KR102306427B1/ko
Priority to AU2018357174A priority patent/AU2018357174B2/en
Priority to US16/647,507 priority patent/US20210363344A1/en
Priority to ES18870964T priority patent/ES2878310T3/es
Publication of WO2019080524A1 publication Critical patent/WO2019080524A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/52—Sports equipment ; Games; Articles for amusement; Toys
    • B29L2031/5281—Articles for amusement
    • B29L2031/529—Toys
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • 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
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention belongs to the technical field of polymer material modification, and particularly relates to a polylactic acid composite material and an application thereof.
  • Polylactic acid resin is a polymer material obtained by chemical synthesis or biosynthesis of lactic acid as a monomer.
  • the raw materials are mainly corn, potato, etc., and the price is low.
  • carbon emissions are extremely small.
  • polylactic acid is non-toxic and non-irritating, has excellent transparency and biodegradability, and is easily catabolized by various microorganisms or enzymes in animals and plants in nature, eventually forming carbon dioxide and water, thus to a certain extent. It reduces white pollution and is an ideal green polymer material.
  • products made of polylactic acid have good biocompatibility, gloss and transparency, and also have certain bacteria resistance and UV resistance. Therefore, they are widely used in medical, spinning, tableware, toys and other fields. .
  • polylactic acid products are mostly disposable products or fast-moving products that do not have strict requirements on the use period. Due to the action of microorganisms, light, radiation, air and the environment of the materials in contact, the polylactic acid products are processed, stored and transported. It is prone to aging degradation during the period, which affects the use of the final product.
  • the present invention can achieve suitable aging properties and excellent biodegradability by controlling the terminal acid group content of the polylactic acid composite material within a certain range.
  • a polylactic acid composite material in parts by weight, comprising the following components:
  • the polylactic acid composite material has a terminal carboxyl group content of 12 to 51 molKOH/t.
  • the method for determining the terminal carboxyl group content is as follows: using a mixture of o-cresol-trichloromethane having a mass ratio of 7:3 as a solvent, and testing the terminal carboxyl group value by using a Metrohm Titrino series automatic potentiometric titrator, and performing the test method FZ/T 50012-2006 "Determination of the carboxyl group content of the middle end of the polyester - titration analysis method", the first value after the decimal point of the carboxyl group value is rounded off according to the method of rounding.
  • the terminal carboxyl group content of the polylactic acid composite material There are many factors affecting the terminal carboxyl group content of the polylactic acid composite material.
  • the microstructure of the raw material polylactic acid is different.
  • the polylactic acid can be obtained by direct polycondensation of lactic acid or ring-opening polymerization of lactide. If the polylactic acid is blocked by using a blocking agent, the polylactic acid synthesized is a polymer containing a certain amount of terminal carboxyl groups. Further, in the polylactic acid synthesis process, by controlling the amount of the catalyst to be added, adjusting the degree of vacuum and the reaction time, the content of the terminal carboxyl group of the synthesized polylactic acid is also affected, so that the microstructure of the polylactic acid is different.
  • the high temperature melting due to the high temperature melting during the modification of the polylactic acid composite, the high temperature melting itself is the balance of further reaction and degradation of the polymer end groups.
  • various additives added, etc. will have a certain influence on the terminal carboxyl group content of the finally prepared polylactic acid composite material, so that the product exhibits different aging properties and biodegradability in macroscopic view.
  • the invention finds that the end carboxyl group content of the polylactic acid composite material is controlled within the range of 12 to 51 mol KOH/t, so that the composite material has suitable aging properties and excellent biodegradability.
  • the higher the terminal carboxyl group content of polylactic acid composites the more likely to degrade after disposal, which is beneficial to reduce environmental pollution.
  • the content of carboxyl groups in polylactic acid composites is too high, which may cause polylactic acid products to be processed, stored and transported. Aging degradation occurs and affects the use of the final product. If the terminal carboxyl group content of the polylactic acid composite is too low, this means that more catalyst, lower vacuum, longer reaction time, and more elaborate equipment and more capital investment are required in the synthesis process. It also produces higher energy consumption. Therefore, preferably, the polylactic acid composite has a terminal acid group content of 18 to 41 molKOH/t; preferably 28 to 36 molKOH/t.
  • the mass melt index MFI of the polylactic acid composite material was tested according to the standard ASTM D1238, and the test conditions were 190 ° C, 2.16 kg, and the unit was g/10 min.
  • the polylactic acid composite material has a biodegradation rate of more than 90% after 12 weeks in a case where the thickness is 2.5 mm or less according to the standard ISO 16929 (2013).
  • the inorganic filler is selected from the group consisting of talc, montmorillonite, kaolin, chalk, calcium carbonate, gypsum, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicate, mica. Mixing one or more; preferably a mixture of one or more of talc, calcium carbonate or silica.
  • the addition of the inorganic filler not only enhances the mechanical properties of the material, but also acts as a nucleating agent to increase the crystallization rate of the polyester composition and improve the processing conditions of the polylactic acid composite material.
  • the plasticizer which is liquid at room temperature is selected from the group consisting of glycerin, polyglycerol, ethylene glycol, polyethylene glycol-400, polyethylene glycol-600, polyethylene glycol-800, epoxy soybean oil, citric acid ester a mixture of one or more of acetyl citrate, triacetyl glyceride, dioctyl adipate.
  • the plasticizers which are liquid at room temperature are mostly low molecular weight compounds.
  • the addition of low molecular weight plasticizers to polylactic acid helps to promote the movement of polylactic acid segments, thereby improving the toughness of polylactic acid composites to some extent.
  • the low molecular weight plasticizer can more effectively promote the crystallization of polylactic acid, and to some extent increase the heat resistant temperature of polylactic acid.
  • the polylactic acid composite further includes 0 to 10 parts by weight of a toughening agent, and the toughening agent is preferably an aliphatic polyester or an aliphatic-aromatic copolyester.
  • the polylactic acid composite material according to the present invention further comprises 0 to 4 parts by weight of the following other auxiliary agents according to the actual performance requirements: a release agent, a surfactant, a wax, an antistatic agent, and a dye. Or other plastic additives.
  • the release agent is: silicone masterbatch, montan wax, erucic acid amide or oleic acid amide;
  • the surfactant is a mixture of one or more of polysorbate, palmitate or laurate;
  • the wax is a mixture of one or more of erucamide, stearic acid amide, behenic acid amide, beeswax or beeswax;
  • the antistatic agent is a permanent antistatic agent, and specifically, a mixture of one or more of PELESTAT-230, PELESTAT-6500, SUNNICO ASA-2500;
  • the dye is a mixture of one or more of carbon black, black species, titanium dioxide, zinc sulfide, indigo blue or fluorescent orange.
  • the other plastic additives may be a nucleating agent, an antifogging agent, a lubricant (such as calcium stearate), a primary antioxidant, a secondary antioxidant, and the like.
  • the invention also provides the application of the above polylactic acid composite material in injection molding grade, plastic grade and extrusion grade products such as tableware, toys and stationery.
  • the invention has the following beneficial effects:
  • the invention predicts the unexpected discovery that the terminal acid group content of the polylactic acid composite material is controlled within the range of 12 to 51 mol KOH/t, and the polylactic acid composite material has a test time of 30 days under the condition of 60 ° C and 60% humidity.
  • the polylactic acid composite material has a biodegradation rate of more than 90% after 12 weeks, and has suitable aging properties and excellent biodegradability.
  • the raw materials used in the present invention are all commercially available.
  • Biodegradation rate according to the standard ISO 16929 (2013), the thickness is less than or equal to 2.5 mm, and the biodegradation rate of the polylactic acid composite after 12 weeks is tested;
  • Mass Melt Index MFI Tested according to standard ASTM D1238, test conditions 190 ° C, 2.16 kg, in g/10 min.
  • the terminal carboxyl group content is determined by using a mixture of o-cresol-trichloromethane with a mass ratio of 7:3 as a solvent, and testing the terminal carboxyl value with a Metrohm Titrino series automatic potentiometric titrator.
  • the test method is performed FZ/T 50012. -2006 "Determination of the carboxyl group content of the middle end of the polyester - titration analysis method", the first value after the decimal point of the terminal acid number is rounded off according to the method of rounding.
  • the terminal acid group value was: 14 mgKOH/g.
  • the terminal acid group value was 19 mgKOH/g.
  • the terminal acid group value was 25 mgKOH/g.
  • the terminal acid group value was 31 mgKOH/g.
  • the terminal acid group value was 36 mgKOH/g.
  • the terminal acid group value was 48 mgKOH/g.
  • the terminal acid group value was: 9 mgKOH/g.
  • polylactic acid, inorganic filler, plasticizer and calcium stearate are uniformly mixed, put into a twin-screw extruder, extruded at 150 °C-220 °C, and granulated to obtain a polylactic acid composite material.
  • the test data is shown in Table 1.
  • the melting index of the composite material can be in a reasonable range under the test condition, and In the case where the thickness is 2.5 mm or less, the polylactic acid composite has a biodegradation rate of more than 90% after 12 weeks, and has suitable aging properties and excellent biodegradability.
  • the polycarboxylate composite has a terminal carboxyl group content of less than 12 molKOH/t, and the composite material has a biodegradation rate of less than 90%; in the comparative example 2, the polycarboxylate composite has a terminal carboxyl group content of more than 51 mol/kg, although the composite material The biodegradation rate is higher, but its melting index rises faster during the test period, and the aging resistance is poor.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种聚乳酸复合材料及其应用，包括组分:i)50-85重量份的聚乳酸；ii)8～35重量份的无机填料；iii)0～8重量份的增塑剂；其中，所述聚乳酸复合材料的端羧基含量为12～51molKOH/t。本发明通过研究意外的发现，将聚乳酸复合材料的端羧基含量控制在12～51molKOH/t范围内，所述聚乳酸复合材料在60℃，60％的湿度的条件下，测试时间30天，质量熔体指数MFI t＝30与初始质量熔体指数MFI t＝0的比3.5<η＝MFI t＝30/MFI t＝0<5.1，说明产品在测试条件下，老化降解慢，且在厚度小于等于2.5mm的情况下，聚乳酸复合材料12周后的生物降解率大于90％，具有合适的老化性能和优良的生物降解性能。

Description

一种聚乳酸复合材料及其应用 技术领域
本发明属于高分子材料改性技术领域，具体涉及一种聚乳酸复合材料及其应用。
背景技术
聚乳酸树脂是一种以乳酸为单体经化学合成或生物合成得到的高分子材料，其原料主要是玉米、马铃薯等，价格低廉，同时由于其原料为自然农作物，因此碳排放极少。从安全性来看，聚乳酸无毒无刺激性，具有优异的透明性和生物降解性能，易被自然界的多种微生物或动植物体内的酶分解代谢，最终形成二氧化碳和水，从而在一定程度上降低了白色污染，是理想的绿色高分子材料。
聚乳酸制成的产品除能生物降解外，生物相容性、光泽度、透明性好，还具有一定的耐菌性和抗紫外性，因此广泛应用于医疗、纺丝、餐具、玩具等领域。
目前聚乳酸产品多为一次性产品或为对使用期限没有特别严格要求的快消品，由于微生物、光照、辐射、空气及所接触的物质环境的作用，导致聚乳酸产品在加工、储存、运输期间容易老化降解，从而影响最终产品的使用。
从上述问题出发，令人惊奇的发现，本发明通过将聚乳酸复合材料的末端酸基含量控制在一定范围内，可以使复合材料具有合适的老化性能和优良的生物降解性能。
发明内容
本发明的目的在于提供一种聚乳酸复合材料，所述聚乳酸复合材料具有合适的老化性能和优良的生物降解性能。
本发明是通过以下技术方案实现的：
一种聚乳酸复合材料，按重量份数计，包括如下组分:
i)50～85重量份的聚乳酸；
ii)8～35重量份的无机填料；
iii)0～8重量份的增塑剂；
其中，所述聚乳酸复合材料的端羧基含量为12～51molKOH/t。
其中，所述端羧基含量的测定方法为：以质量比7∶3的邻甲酚--三氯甲烷混合液为溶剂，用瑞士万通Titrino系列自动电位滴定仪测试端羧基值，测试方法执行FZ/T 50012-2006《聚酯中端羧基含量的测定-滴定分析法》，端羧基值小数点后第一位数值根据四舍五入的方法，取整数。
影响聚乳酸复合材料的端羧基含量的因素有很多，如原料聚乳酸的微观结构不同，本领域技术人员公知的，聚乳酸可以通过乳酸直接缩聚或者通过丙交酯开环聚合得到，合成过程中，如未使用封端剂对聚乳酸进行封端处理，合成得到的聚乳酸为含有一定量端羧基的聚合物。另外，在聚乳酸合成过程中，通过控制催化剂的加入量，调整真空度以及反应时间，也会对合成的聚乳酸的端羧基的含量产生影响，从而使聚乳酸的微观结构不同。由于聚乳酸复合材料的改性过程中进行了高温熔融，高温熔融本身就是聚合物端基进一步反应和降解的平衡。再加上加入的各种助剂等，都会对最终制备得到的聚乳酸复合材料的端羧基含量产生一定的影响，从而产品在宏观上表现出不同的老化性能和生物降解性能。
本发明通过研究发现，将聚乳酸复合材料的端羧基含量控制在12～51molKOH/t范围内，可以使复合材料具有合适的老化性能和优良的生物降解性能。聚乳酸复合材料的端羧基含量越高，废弃后更容易发生降解，有利于降低环境污染，但聚乳酸复合材料中端羧基的含量过高，可能导致聚乳酸产品在加工、储存、运输期间即发生了老化降解，而影响了最终产品的使用。如果聚乳酸复合材料的端羧基含量过低，这意味着在合成过程中需要更多的催化剂，更低的真空，更长的反应时间，同时需要更加精细的设备和更多资金的投入，同时也会产生更高的能耗。因此，优选的，所述聚乳酸复合材料的末端酸基含量为18～41molKOH/t；优选为28～36molKOH/t。
所述的聚乳酸复合材料，在60℃，60％的湿度的条件下，测试时间30天，质量熔体指数MFI t＝30与初始质量熔体指数MFI t＝0的比值满足如下关系；
3.5<η＝MFI t＝30/MFI t＝0<5.1；
优选为：3.9<η＝MFI t＝30/MFI t＝0<4.7；
更优选为：4.2<η＝MFI t＝30/MFI t＝0<4.5；
所述聚乳酸复合材料的质量熔体指数MFI根据标准ASTM D1238测试，测试条件为190℃，2.16kg，单位为g/10min。
所述的聚乳酸复合材料，根据标准ISO 16929(2013)，在厚度小于等于2.5mm的情况下，所述聚乳酸复合材料12周后的生物降解率大于90％。
所述无机填料选自滑石粉、蒙脱土、高岭土、白垩、碳酸钙、石膏、氯化钙、氧化铁、白云石、二氧化硅、硅灰石、二氧化钛、硅酸盐、云母中的一种或几种的混合；优选为滑石粉、碳酸钙或二氧化硅中的一种或几种的混合。无机填料的加入不仅可以提升材料的机械性能，而且可以作为成核剂，提升聚酯组合物的结晶速率，改善聚乳酸复合材料的加工条件。
所述室温下为液体的增塑剂选自甘油、聚甘油、乙二醇、聚乙二醇-400、聚乙二醇-600、聚乙二醇-800、环氧大豆油、柠檬酸酯、乙酰柠檬酸酯、三乙酰甘油酯、己二酸二辛酯中的一种或几种的混合。
室温下呈液体的增塑剂多为低分子量化合物，低分子量增塑剂加入聚乳酸中，有助于促进聚乳酸链段的运动，从而在一定程度上提高聚乳酸复合材料的韧性。同时，低分子量增塑剂能够更有效的促进聚乳酸的结晶，在一定程度上提高聚乳酸的耐热温度。
所述聚乳酸复合材料还包括0至10重量份的增韧剂，所述增韧剂优选为脂肪族聚酯或脂肪族-芳香族共聚酯。
根据实际性能需要，本发明所述的聚乳酸复合材料，按重量份数计，还包括0至4重量份的下述其他助剂：脱模剂、表面活性剂、蜡、防静电剂、染料或其他塑料添加剂。
所述脱模剂为：硅酮母粒、蒙坦蜡、芥酸酰胺或油酸酰胺；
所述表面活性剂为聚山梨醇酯、棕榈酸酯或月桂酸酯中的一种或者几种的混合；
所述蜡为芥酸酰胺、硬脂酰胺、山嵛酸酰胺、蜂蜡或蜂蜡酯中的一种或者几种的混合；
所述防静电剂为永久性抗静电剂，具体可以列举出PELESTAT-230、PELESTAT-6500、SUNNICO ASA-2500中的一种或者几种的混合；
所述染料为炭黑、黑种、钛白粉、硫化锌、酞青蓝或荧光橙中的一种或者几种的混合。
所述其他塑料添加剂可以为成核剂、防雾剂、润滑剂(如硬脂酸钙)、主抗氧剂、辅抗氧剂等。
本发明还提供了上述的一种聚乳酸复合材料在餐具、玩具、文具等注塑级、吸塑级、挤出级产品中的应用。
本发明与现有技术相比，具有如下有益效果：
本发明通过研究意外的发现，将聚乳酸复合材料的末端酸基含量控制在12～51molKOH/t范围内，所述聚乳酸复合材料在60℃，60％的湿度的条件下，测试时间30天，质量熔体指数MFI t＝30与初始质量熔体指数MFI t＝0的比值3.5<η＝MFI t＝30/MFI t＝0<5.1说明产品在测试条件下，老化降解慢；且在厚度小于等于2.5mm的情况下，所述聚乳酸复合材料12周后的生物降解率大于90％，具有合适的老化性能和优良的生物降解性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
本发明所采用的原料均来源于市购。
性能测试方法：
生物降解率：根据标准ISO 16929(2013)，厚度小于等于2.5mm，测试聚乳酸复合材料12周后的生物降解率；
η：在60℃，60％的湿度的条件下，测试时间30天，质量熔体指数MFI t＝30与初始质量熔体指数MFI t＝0的比值，η＝MFI t＝30/MFI t＝0，η值越低，说明产品的老化降解慢，耐老化性能好；
质量熔体指数MFI：根据标准ASTM D1238测试，测试条件为190℃，2.16kg，单位为g/10min。
端羧基含量的测定方法为：以质量比7∶3的邻甲酚--三氯甲烷混合液为溶剂，用瑞士万通Titrino系列自动电位滴定仪测试端羧基值，测试方法执行FZ/T 50012-2006《聚酯中端羧基含量的测定-滴定分析法》，端酸基值小数点后第一位数值根据四舍五入的方法，取整数。
聚乳酸的合成：
实施例A1
取20mol的市售L-丙交酯为原料，以甲苯作为有机溶液，加入0.035mol的辛酸亚锡作为催化剂，加入到20L的不锈钢反应釜中，减压至高真空0.080MPa，缓慢加热至145℃，搅拌1h使丙交酯完全溶解。抽取由于加热产生的甲苯蒸汽，维持真空为0.080MPa，145℃恒温反应18h后停止反应；待反应釜压力为常压后，加入乙酸乙酯溶解反应釜中的固体，倒入容器中风干，待溶剂乙酸乙酯完全挥发完后，至于真空干燥器中备用。
末端酸基值为：14mgKOH/g。
单产耗电：85kw·h/Kg。
实施例A2
取20mol的市售L-丙交酯为原料，以甲苯作为有机溶液，加入0.035mol的辛酸亚锡作为催化剂，加入到20L的不锈钢反应釜中，减压至高真空0.080MPa，缓慢加热至145℃，搅拌1h使丙交酯完全溶解。抽取由于加热产生的甲苯蒸汽，维持真空为0.080MPa，145℃恒温反应13h后停止反应；待反应釜压力为常压后，加入乙酸乙酯溶解反应釜中的固体，倒入容器中风干，待溶剂乙酸乙酯完全挥发完后，至于真空干燥器中备用。
末端酸基值为：19mgKOH/g。
单产耗电：63kw·h/Kg。
实施例A3
取20mol的市售L-丙交酯为原料，以甲苯作为有机溶液，加入0.027mol的辛酸亚锡作为催化剂，加入到20L的不锈钢反应釜中，减压至高真空0.101MPa，缓慢加热至135℃，搅拌1h使丙交酯完全溶解。抽取由于加热产生的甲苯蒸汽，维持真空为0.101MPa，135℃恒温反应12h后停止反应；待反应釜压力为常压后，加入乙酸乙酯溶解反应釜中的固体，倒入容器中风干，待溶剂乙酸乙酯完全挥发完后，至于真空干燥器中备用。
末端酸基值为：25mgKOH/g。
单产耗电：60kw·h/Kg。
实施例A4
取20mol的市售L-丙交酯为原料，以甲苯作为有机溶液，加入0.027mol的辛酸亚锡作为催化剂，加入到20L的不锈钢反应釜中，减压至高真空0.101MPa，缓慢加热至135℃，搅拌1h使丙交酯完全溶解。抽取由于加热产生的甲苯蒸汽，维持真空为0.101MPa，135℃恒温反应9h后停止反应；待反应釜压力为常压后，加入乙酸乙酯溶解反应釜中的固体，倒入容器中风干，待溶剂乙酸乙酯完全挥发完后，至于真空干燥器中备用。
末端酸基值为：31mgKOH/g。
单产耗电：52kw·h/Kg。
实施例A5
取20mol的市售L-丙交酯为原料，以甲苯作为有机溶液，加入0.022mol的辛酸亚锡作为催化剂，加入到20L的不锈钢反应釜中，减压至高真空0.150MPa，缓慢加热130℃，搅拌1h使丙交酯完全溶解。抽取由于加热产生的甲苯蒸汽，维持真空为0.150MPa，130℃恒温反应9h后停止反应；待反应釜压力为常压后，加入乙酸乙酯溶解反应釜中的固体，倒入容器中风干，待溶剂乙酸乙酯完全挥发完后，至于真空干燥器中备用。
末端酸基值为：36mgKOH/g。
单产耗电：50kw·h/Kg。
对比例B1:
取20mol的市售L-丙交酯为原料，以甲苯作为有机溶液，加入0.022mol的辛酸亚锡作为催化剂，加入到20L的不锈钢反应釜中，减压至高真空0.150MPa，缓慢加热至130℃，搅拌1h使丙交酯完全溶解。抽取由于加热产生的甲苯蒸汽，维持真空为0.150MPa，130℃恒温反应6h后停止反应；待反应釜压力为常压后，加入乙酸乙酯溶解反应釜中的固体，倒入容器中风干，待溶剂乙酸乙酯完全挥发完后，至于真空干燥器中备用。
末端酸基值为：48mgKOH/g。
单产耗电：36kw·h/Kg。
对比例B2:
取20mol的市售L-丙交酯为原料，以甲苯作为有机溶液，加入0.035mol的辛酸亚锡作为催化剂，加入到20L的不锈钢反应釜中，减压至高真空0.065MPa，缓慢加热至145℃，搅拌1h使丙交酯完全溶解。抽取由于加热产生的甲苯蒸汽，维持真空为0.065MPa，145℃恒温反应21h后停止反应；待反应釜压力为常压后，加入乙酸乙酯溶解反应釜中的固体，倒入容器中风干，待溶剂乙酸乙酯完全挥发完后，至于真空干燥器中备用。
末端酸基值为：9mgKOH/g。
单产耗电：92kw·h/Kg。
按表1配方将聚乳酸、无机填料、增塑剂和硬脂酸钙混合均匀后，投入双螺杆挤出机中，于150℃-220℃挤出、造粒，得到聚乳酸复合材料，性能测试数据如表1所示。
表1 实施例1-10及对比例1-2的性能测试结果(重量份)
Figure PCTCN2018092804-appb-000001
由表1结果可以看出，本发明实施例通过将聚乳酸复合材料的端羧基含量控制在12～51 molKOH/t范围内，可以使复合材料的熔指在测试条件下处于合理的范围，且在厚度小于等于2.5mm的情况下，所述聚乳酸复合材料12周后的生物降解率大于90％，具有合适的老化性能和优良的生物降解性能。对比例1中聚乳酸复合材料的端羧基含量低于12molKOH/t，复合材料的生物降解率低于90％；对比例2中聚乳酸复合材料的端羧基含量高于51mol/kg，虽然复合材料的生物降解率较高，但其熔指在测试周期内升高较快，耐老化性能较差。

Claims (10)

  1. 一种聚乳酸复合材料，其特征在于，按重量份计，包括如下组分:
    i)50～85重量份的聚乳酸；
    ii)8～35重量份的无机填料；
    iii)0～8重量份的增塑剂；
    其中，所述聚乳酸复合材料的端羧基含量为12～51molKOH/t。
  2. 根据权利要求1所述的聚乳酸复合材料，其特征在于，所述端羧基含量的测定方法为：以质量比7∶3的邻甲酚--三氯甲烷混合液为溶剂，用瑞士万通Titrino系列自动电位滴定仪测试端羧基值，测试方法执行FZ/T 50012-2006《聚酯中端羧基含量的测定-滴定分析法》，端羧基值小数点后一位数值根据四舍五入的方法，取整数。
  3. 根据权利要求1所述的聚乳酸复合材料，其特征在于，所述聚乳酸复合材料的端羧基含量为18～41molKOH/t，优选为28～36molKOH/t。
  4. 根据权利要求1所述的聚乳酸复合材料，其特征在于，在60℃，60％的湿度的条件下，测试时间30天，所述聚乳酸复合材料的质量熔体指数MFI t＝30与初始质量熔体指数MFI t＝0的比值满足如下关系；
    3.5<η＝MFI t＝30/MFI t＝0<5.1；
    优选为：3.9<η＝MFI t＝30/MFI t＝0<4.7；
    更优选为：4.2<η＝MFI t＝30/MFI t＝0<4.5；
    所述聚乳酸复合材料的质量熔体指数MFI根据标准ASTM D1238测试，测试条件为190℃，2.16kg，单位为g/10min。
  5. 根据权利要求1所述的聚乳酸复合材料，其特征在于，根据标准ISO 16929(2013)，在厚度小于等于2.5mm的情况下，所述聚乳酸复合材料12周后的生物降解率大于90％。
  6. 根据权利要求1所述的聚乳酸复合材料，其特征在于，所述无机填料选自滑石粉、蒙脱土、高岭土、白垩、碳酸钙、石膏、氯化钙、氧化铁、白云石、二氧化硅、硅灰石、二氧化钛、硅酸盐、云母中的一种或几种的混合；优选为滑石粉、碳酸钙或二氧化硅中的一种或几种的混合。
  7. 根据权利要求1所述的聚乳酸复合材料，其特征在于，所述室温下为液体的增塑剂选自甘油、聚甘油、乙二醇、聚乙二醇-400、聚乙二醇-600、聚乙二醇-800、环氧大豆油、柠檬酸酯、乙酰柠檬酸酯、三乙酰甘油酯、己二酸二辛酯中的一种或几种的混合。
  8. 根据权利要求1所述的聚乳酸复合材料，其特征在于，按重量份计，所述聚乳酸复合材料还包括0-10重量份的增韧剂，所述增韧剂为脂肪族聚酯或脂肪族-芳香族共聚酯。
  9. 根据权利要求1所述的聚乳酸复合材料，其特征在于，按重量份计，所述聚乳酸复合材料还包括0至4重量份的下述其他助剂：脱模剂、表面活性剂、蜡、防静电剂、染料、或其他塑料添加剂。
  10. 权利要求1-9任一项所述的聚乳酸复合材料在餐具、玩具、文具等注塑级、吸塑级、挤出级产品中的应用。
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