WO2017152678A1 - 一种可生物降解聚酯组合物 - Google Patents

一种可生物降解聚酯组合物 Download PDF

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WO2017152678A1
WO2017152678A1 PCT/CN2016/110000 CN2016110000W WO2017152678A1 WO 2017152678 A1 WO2017152678 A1 WO 2017152678A1 CN 2016110000 W CN2016110000 W CN 2016110000W WO 2017152678 A1 WO2017152678 A1 WO 2017152678A1
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Prior art keywords
polyester composition
biodegradable polyester
cyclopentanone
ppm
biodegradable
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PCT/CN2016/110000
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English (en)
French (fr)
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卢昌利
袁志敏
蔡彤旻
黄险波
曾祥斌
焦健
苑仁旭
钟宇科
熊凯
杨晖
麦开锦
董学腾
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杨红梅
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=56156492&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2017152678(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 杨红梅 filed Critical 杨红梅
Priority to JP2018511325A priority Critical patent/JP6471264B2/ja
Priority to EP16893321.6A priority patent/EP3260494B1/en
Priority to US15/578,249 priority patent/US10364320B2/en
Priority to AU2016396710A priority patent/AU2016396710B2/en
Priority to KR1020177034905A priority patent/KR101998502B1/ko
Priority to ES16893321T priority patent/ES2874151T3/es
Publication of WO2017152678A1 publication Critical patent/WO2017152678A1/zh

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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
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    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/26Carbonates; Bicarbonates
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
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    • C08K5/10Esters; Ether-esters
    • C08K5/11Esters; Ether-esters of acyclic polycarboxylic acids
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02Starch; Degradation products thereof, e.g. dextrin
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    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08L2205/00Polymer mixtures characterised by other features
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    • C08L2205/00Polymer mixtures characterised by other features
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    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the invention belongs to the field of polymer material modification, and in particular relates to a biodegradable polyester composition having excellent bubble stability.
  • Biodegradable polyester is a kind of polymer material which is made from biological resources. Compared with petroleum-based polymers based on petrochemical resources, biodegradable polyesters can be degraded in biological or biochemical processes or in biological environments. It is currently the most active and market-based degradation in biodegradable plastics research. One of the materials.
  • Biodegradable polyester film is one of the important application fields of biodegradable polyester, including food bags, garbage bags, shopping bags and plastic film.
  • the biodegradable polyester In the process of preparing a film by blow molding, the biodegradable polyester often has a phenomenon that the film is not sufficiently lubricated and adhered to the roller or is too lubricious to be wound up, resulting in poor bubble stability during film blowing, and the film thickness is extremely poor. The phenomenon has seriously affected the continuity of the blown film.
  • Patent CN 101622311A by adding 0.05-5 wt% biodiesel to the biodegradable polyester mixture, by reducing the viscosity of the polyester mixture, to some extent, the film sticks to the roller, thereby ensuring continuous film blowing. Sex.
  • the decrease in the viscosity of the polyester mixture indicates that the addition of biodiesel impairs the properties of the polyester to some extent, resulting in an increase in the melting index of the polyester mixture and a decrease in viscosity.
  • biodegradable polyesters have significantly improved blown film properties by the addition of trace amounts of cyclopentanone, and films are blown at higher speeds.
  • the foam stability is good, and the thickness of the film is extremely small, which ensures the continuity of the blown film production.
  • a biodegradable polyester composition comprising, by weight, components:
  • the cyclopentanone is contained in an amount of from 0.5 ppm to 85 ppm, preferably from 5 ppm to 50 ppm, more preferably from 10 ppm to 35 ppm, based on the total mass of the biodegradable polyester composition.
  • the biodegradable polyester composition comprises, by weight, components:
  • the weight content of the cyclopentanone of the present invention is tested by accurately weighing 1.2000 g of the biodegradable polyester composition into a static headspace test bottle and testing the ring of the biodegradable polyester composition by a static headspace method.
  • the peak area of pentanone can be calculated from the peak area of cyclopentanone in the biodegradable polyester composition and the cyclopentanone standard curve to calculate the content of cyclopentanone in the biodegradable polyester composition; the standard curve is from cyclopentanone / Calibration of methanol solution.
  • the biodegradable aliphatic-aromatic polyester is polybutylene terephthalate PBAT, polysuccinate terephthalate PBST or polysebacate terephthalate.
  • cyclopentanone to the biodegradable polyester can act like a lubricant, but if the content of cyclopentanone in the biodegradable polyester composition is too high, the film is too lubricated during high-speed film blowing, resulting in The film does not wind up well on the roll, which also causes the bubble to become unstable.
  • the present inventors have found that controlling the content of cyclopentanone in the biodegradable polyester composition at 0.5 ppm to 85 ppm can improve the degree of lubrication of the biodegradable polyester during the blow molding process, at the film blowing speed.
  • the film thickness is extremely poor ⁇ 0.2 ⁇ m, and the film thickness relative deviation is ⁇ 1%, which ensures the stability of the bubble and the continuity of the blown film.
  • the weight content of cyclopentanone is preferably from 5 ppm to 50 ppm, more preferably from 10 ppm to 35 ppm, based on the total weight of the biodegradable polyester composition.
  • the organic filler is selected from one of natural starch, plasticized starch, modified starch, natural fiber or wood flour or a mixture thereof;
  • the inorganic filler is selected from the group consisting of talc, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicic acid.
  • talc montmorillonite
  • kaolin chalk
  • calcium carbonate graphite
  • gypsum conductive carbon black
  • calcium chloride iron oxide
  • dolomite silica
  • wollastonite titanium dioxide
  • silicic acid silicic acid.
  • salt mica, fiberglass or mineral fiber or a mixture thereof.
  • the route of obtaining the cyclopentanone of the present invention can be directly added to the cyclopentanone during the blending and extrusion process of the biodegradable polyester composition.
  • the biodegradable polyester composition of the present invention may further comprise 0 to 4 parts of at least one of the following materials: a plasticizer, a mold release agent, a surfactant, a wax, an antistatic agent, according to different needs of the use. Dyes, UV absorbers, UV stabilizers or other plastic additives.
  • the plasticizer is one or a mixture of two or more of citrate, glycerin, epoxidized soybean oil or the like;
  • the release agent is one of silicone oil, paraffin wax, white mineral oil, petrolatum or a mixture of two or more;
  • the surfactant is one or a mixture of two or more of polysorbate, palmitate or laurate;
  • the wax is one or a mixture of two or more of erucamide, stearic acid amide, behenic acid amide, beeswax or beeswax;
  • the antistatic agent is a permanent antistatic agent, and specifically one of PELESTAT-230, PELESTAT-6500, SUNNICO ASA-2500 or a mixture of two or more;
  • the dye is one of carbon black, black species, titanium white powder, zinc sulfide, indigo blue, fluorescent orange or a mixture of two or more.
  • the UV absorber is one or more of UV-944, UV-234, UV531, UV326;
  • the UV stabilizer is one or more of UV-123, UV-3896, UV-328;
  • the other plastic additive may be a nucleating agent, an antifogging agent, or the like;
  • the biodegradable polyester composition of the invention can be used for preparing shopping bags, compost bags, mulch films, protective covering films, silo films, film strips, fabrics, non-woven fabrics, textiles, fishing nets, load-bearing bags, garbage bags, etc. .
  • the invention has the following beneficial effects:
  • the present invention can improve the degree of lubrication of the biodegradable polyester composition during the blow molding process by adding cyclopentanone to the composition and controlling the content of the cyclopentanone in the composition to be in the range of 0.5 ppm to 85 ppm.
  • the film speed is 176 Kg/h
  • the film thickness is extremely poor ⁇ 0.2 ⁇ m
  • the film thickness relative deviation is ⁇ 1%, which has excellent bubble stability and ensures the continuity of the blown film.
  • i) selects PBAT; component iv) selects ADR4370; organic filler selects starch; inorganic filler selects talc powder, calcium carbonate; plasticizer selects citric acid ester; surfactant selects palmitate; wax selects erucic acid Amide; the above auxiliary agents, PBAT, ADR4370, PLA, and cyclopentanone are all commercially available.
  • the bubble stability during the blown film process of the biodegradable polyester composition is determined by the extremely poor thickness of the film and the relative deviation of the thickness of the film.
  • the film thickness was measured by a spiral micrometer: 10 measurement points were uniformly taken on a film of 1 m*1 m for measurement.
  • the film thickness difference is the difference between the maximum thickness value and the minimum thickness value among the 10 measurement points.
  • the relative deviation of the film thickness is calculated by the following formula:
  • cyclopentanone methanol solution Preparation of cyclopentanone methanol solution at concentrations of 0.0001 g/L, 0.001 g/L, 0.01 g/L, 0.1 g/L, 5.0 g/L, 10.0 g/L, 20.0 g/L, respectively, by static headspace method
  • the peak areas of cyclopentanone in the above different concentrations of cyclopentanone methanol solution were tested, and the standard curve of cyclopentanone was prepared by taking the peak area of cyclopentanone as the ordinate and the concentration of cyclopentanone as the abscissa.
  • the static headspace test conditions are as follows:
  • Heating box 105 ° C
  • the content of cyclopentanone in the biodegradable polyester composition in the examples was 0.5 to 85 ppm, and when the film blowing speed was 176 kg/h, the film thickness was extremely poor ⁇ 0.2 ⁇ m, and the film thickness was relatively The deviation ⁇ 1% indicates that the composition has better bubble stability, while the comparative example 1 does not add cyclopentanone.
  • the content of cyclopentanone in the comparative example 2 exceeds 85 ppm, the film thickness is extremely poor > 0.2 ⁇ m, and the film thickness is relatively different. >1% indicates that the composition is unstable.
  • the film blowing speed of Comparative Example 3 was lower than 176 Kg/h, the film blowing speed of Comparative Example 4 was higher than 176 Kg/h, the film thickness was extremely poor > 0.2 ⁇ m, the relative deviation of the film thickness was >1%, and the bubble of the composition was also less. stable.

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

本发明公开了一种可生物降解聚酯组合物,其中,基于可生物降解聚酯组合物的总重量计,环戊酮的重量含量为0.5ppm-85ppm;本发明通过在组合物中添加环戊酮,将组合物中环戊酮的含量控制在0.5ppm-85ppm范围内,可以改善可生物降解聚酯组合物在吹塑过程中膜的润滑程度,在吹膜速度为176Kg/h时,膜厚极差<0.2μm,膜厚相对偏差<1%,保证了膜泡的稳定性和吹膜的连续性。

Description

一种可生物降解聚酯组合物 技术领域
本发明属于高分子材料改性领域,具体涉及一种具有优异膜泡稳定性的可生物降解聚酯组合物。
背景技术
可生物降解聚酯是以生物资源为原料的一类高分子材料。相对于以石化资源为原料的石油基高分子,可生物降解聚酯能够在生物或生物化学作用过程中或生物环境中发生降解,是目前生物降解塑料研究中非常活跃和市场应用最好的降解材料之一。
可生物降解聚酯薄膜是目前可生物降解聚酯重要应用领域之一,主要包括食品袋、垃圾袋、购物袋和地膜等。可生物降解聚酯在吹塑制备薄膜的过程中,经常会出现薄膜不够润滑粘于辊上或过于润滑无法收卷的现象,从而导致吹膜过程中膜泡稳定性差,膜材厚度极差大的现象,严重影响了吹膜的连续性。专利CN 101622311A通过在可生物降解聚酯混合物中加入0.05-5重量%的生物柴油,通过降低聚酯混合物的粘度,在一定程度上减轻了薄膜粘于辊上的现象,保证了吹膜的连续性。但聚酯混合物粘度的降低,说明生物柴油的加入在一定程度上损害了聚酯的性能,导致聚酯混合物熔指升高,粘度降低。
本发明经研究惊讶地发现,在可生物降解聚酯组合物中,通过添加微量的环戊酮,可以使可生物降解聚酯具有明显改善的吹膜特性,在较高速度吹膜时,膜泡稳定性好,膜材厚度极差较小,保证了吹膜生产的连续性。
发明内容
本发明的目的在于提供一种可生物降解聚酯组合物,通过在该组合物中添加微量的环戊酮,可以使制备得到的可生物降解聚酯组合物具有优异的膜泡稳定性。
本发明是通过以下技术方案实现的:
一种可生物降解聚酯组合物,按重量份计,包括组分:
i)60至99份的可生物降解的脂族-芳族聚酯;
ii)0至40份的聚乳酸;
iii)0至30份的有机填料和/或无机填料;
iv)0至1份的含有环氧基团且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物。
其中,基于可生物降解聚酯组合物的总重量计,环戊酮的重量含量为0.5ppm-85ppm,优选为5ppm-50ppm,更优选为10ppm-35ppm。
优选的,所述的一种可生物降解聚酯组合物,按重量份计,包括组分:
i)65至95份的可生物降解的脂族-芳族聚酯;
ii)5至35份的聚乳酸;
iii)5至25份的有机填料和/或无机填料;
iv)0.02至0.5份的含有环氧基团且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物。
本发明所述环戊酮的重量含量采用如下方法测试:精确称量1.2000g的可生物降解聚酯组合物加入静态顶空测试瓶中,通过静态顶空方法测试可生物降解聚酯组合物中环戊酮的峰面积,根据可生物降解聚酯组合物中环戊酮的峰面积和环戊酮标准曲线即可计算得到可生物降解聚酯组合物中环戊酮的含量;标准曲线由环戊酮/甲醇溶液标定。
所述可生物降解的脂族-芳族聚酯为聚己二酸对苯二甲酸丁二醇酯PBAT、聚琥珀酸对苯二甲酸丁二醇酯PBST或聚癸二酸对苯二甲酸丁二醇酯PBSeT中的一种或几种。
环戊酮添加到可生物降解聚酯中,可以起到类似润滑剂的作用,但若可生物降解聚酯组合物中环戊酮的含量过高,在高速吹膜过程中,膜过于润滑,导致膜无法很好的在辊上收卷,同样会导致膜泡不稳。而本发明通过研究发现,将可生物降解聚酯组合物中的环戊酮的含量控制在0.5ppm-85ppm,可以改善可生物降解聚酯在吹塑过程中膜的润滑程度,在吹膜速度为176Kg/h时,膜厚极差<0.2μm,膜厚相对偏差<1%,保证了膜泡的稳定性和吹膜的连续性。
基于可生物降解聚酯组合物的总重量,环戊酮的重量含量优选为5ppm-50ppm,更优选为10ppm-35ppm。
所述有机填料选自天然淀粉、塑化淀粉、改性淀粉、天然纤维或木粉中的一种或其混合物;
所述无机填料选自滑石粉、蒙脱土、高岭土、白垩、碳酸钙、石墨、石膏、导电炭黑、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、玻璃纤维或矿物纤维中的一种或其混合物。
本发明所述环戊酮的获得途径,可以通过在可生物降解聚酯组合物共混挤出加工的过程中直接添加环戊酮。
根据不同的用途需要,本发明的可生物降解聚酯组合物还可以进一步加入0至4份的至少一种下述物质:增塑剂、脱模剂、表面活性剂、蜡、防静电剂、染料、UV吸收剂、UV稳定剂或其他塑料添加剂。
所述增塑剂为柠檬酸酯、甘油、环氧大豆油等中的一种或者两种及以上的混合物;
所述脱模剂为硅油、石蜡、白矿油、凡士林中的一种或者两种及以上的混合物;
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两种及以上的混合物;
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两种及以上的混合物;
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中的一种或者两种及以上的混合物;
所述染料为炭黑、黑种、钛白粉、硫化锌、酞青蓝、荧光橙中的一种或者两种及以上的混合物。
所述UV吸收剂为UV-944、UV-234、UV531、UV326中的一种或几种;
所述UV稳定剂为UV-123、UV-3896、UV-328中的一种或几种;
所述其他塑料添加剂可以为成核剂、防雾剂等;
本发明所述的可生物降解聚酯组合物可用于制备购物袋、堆肥袋、地膜、保护性覆盖膜、筒仓膜、薄膜带、织物、非织物、纺织品、渔网、承重袋、垃圾袋等。
本发明与现有技术相比,具有如下有益效果:
本发明通过在组合物中添加环戊酮,将组合物中环戊酮的含量控制在0.5ppm-85ppm范围内,可以改善可生物降解聚酯组合物在吹塑过程中膜的润滑程度,在吹膜速度为176Kg/h时,膜厚极差<0.2μm,膜厚相对偏差<1%,具有优异的膜泡稳定性,保证了吹膜的连续性。
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。
本发明实施例i)选用PBAT;组分iv)选用ADR4370;有机填料选用淀粉;无机填料选用滑石粉、碳酸钙;增塑剂选用柠檬酸酯;表面活性剂选用棕榈酸酯;蜡选用芥酸酰胺;上述助剂、PBAT、ADR4370及PLA、环戊酮均来源于市购。
实施例1-16及对比例1-4:
按表1所示配方,将PBAT、PLA、ADR4370、有机填料、无机填料、增塑剂、表面活性剂、蜡等助剂以及环戊酮混匀后投入单螺杆挤出机中,于140℃-240℃挤出、造粒,得到组合物。性能测试数据见表1。
性能评价方法:
(1)可生物降解聚酯组合物膜泡稳定性的评估方法:
可生物降解聚酯组合物吹膜过程中的膜泡稳定性通过膜材厚度极差和膜材厚度相对偏差的方 法进行评估:
薄膜厚度用螺旋测微计测试:在1m*1m的薄膜上均匀取10个测量点进行测量。
膜厚极差为10个测量点中最大厚度值与最小厚度值的差值。
膜厚相对偏差按下式计算:
Figure PCTCN2016110000-appb-000001
其中平均膜厚在1m*1m的薄膜上均匀取10个测量点,分别测试厚度后取算数平均值。(2)环戊酮的测定方法:
1)环戊酮标准曲线的制作:
配制浓度分别为0.0001g/L、0.001g/L、0.01g/L、0.1g/L、5.0g/L、10.0g/L、20.0g/L的环戊酮甲醇溶液,通过静态顶空方法分别测试上述不同浓度环戊酮甲醇溶液中环戊酮的峰面积,以环戊酮的峰面积为纵坐标,环戊酮的浓度为横坐标,制作环戊酮的标准曲线。
2)可生物降解聚酯组合物中环戊酮含量的测定:
精确称量1.2000g左右的可生物降解聚酯组合物加入静态顶空测试瓶中,通过静态顶空方法测试可生物降解聚酯组合物中环戊酮的峰面积,根据可生物降解聚酯组合物中环戊酮的峰面积和环戊酮标准曲线即可计算得到可生物降解聚酯组合物中环戊酮的含量。
静态顶空所用仪器型号和参数如下:
Agilent Technologies 7697 Headspace Sampler;
Agilent Technologies 7890A GC System;
色谱柱:J&W 122-7032:250℃:30m x 250μm x 0.25μm
进样:前SS进样口N2
出样:前检测器FID。
静态顶空测试条件如下:
温度:
加热箱:105℃
定量环:135℃
传输线:165℃
时间:
样品瓶平衡:120分钟
进样持续时间:0.09分钟
GC循环:30分钟。
表1对比例1~4和实施例1-16测试数据(重量份)
Figure PCTCN2016110000-appb-000002
续表1
Figure PCTCN2016110000-appb-000003
从表1中可以看出,实施例中的可生物降解聚酯组合物中环戊酮的含量为0.5-85ppm,在吹膜速度为176Kg/h时,膜厚极差<0.2μm,膜厚相对偏差<1%,表明组合物具有更好的膜泡稳定性,而对比例1未加入环戊酮,对比例2环戊酮含量超出85ppm时,膜厚极差>0.2μm,膜厚相对偏差>1%,表明组合物的膜泡不稳定。对比例3的吹膜速度低于176Kg/h,对比例4的吹膜速度高于176Kg/h,膜厚极差>0.2μm,膜厚相对偏差>1%,组合物的膜泡也较不稳定。

Claims (8)

  1. 一种可生物降解聚酯组合物,其特征在于,按重量份计,包括组分:
    i)60至99份的可生物降解的脂族-芳族聚酯;
    ii)0至40份的聚乳酸;
    iii)0至30份的有机填料和/或无机填料;
    iv)0至1份的含有环氧基团且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物。
  2. 根据权利要求1所述的一种可生物降解聚酯组合物,其特征在于,基于可生物降解聚酯组合物的总重量计,环戊酮的重量含量为0.5ppm-85ppm,优选为5ppm-50ppm,更优选为10ppm-35ppm。
  3. 根据权利要求1或2所述的一种可生物降解聚酯组合物,其特征在于,按重量份计,包括组分:
    i)65至95份的可生物降解的脂族-芳族聚酯;
    ii)5至35份的聚乳酸;
    iii)5至25份的有机填料和/或无机填料;
    iv)0.02至0.5份的含有环氧基团且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物。
  4. 根据权利要求2或3所述的一种可生物降解聚酯组合物,其特征在于,所述环戊酮的重量含量采用如下方法测试:精确称量1.2000g的可生物降解聚酯组合物加入静态顶空测试瓶中,通过静态顶空方法测试可生物降解聚酯组合物中环戊酮的峰面积,根据可生物降解聚酯组合物中环戊酮的峰面积和环戊酮标准曲线即可计算得到可生物降解聚酯组合物中环戊酮的含量;标准曲线由环戊酮/甲醇溶液标定。
  5. 根据权利要求1-3任一项所述的一种可生物降解聚酯组合物,其特征在于,所述可生物降解的脂族-芳族聚酯为聚己二酸对苯二甲酸丁二醇酯PBAT、聚琥珀酸对苯二甲酸丁二醇酯PBST或聚癸二酸对苯二甲酸丁二醇酯PBSeT中的一种或几种。
  6. 根据权利要求1-3任一项所述的一种可生物降解聚酯组合物,其特征在于,所述有机填料选自天然淀粉、塑化淀粉、改性淀粉、天然纤维或木粉中的一种或其混合物;所述无机填料选自滑石粉、蒙脱土、高岭土、白垩、碳酸钙、石墨、石膏、导电炭黑、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、玻璃纤维或矿物纤维中的一种或其混合物。
  7. 根据权利要求1-3任一项所述的一种可生物降解聚酯组合物,其特征在于,还包括0至4份的至少一种下述物质:增塑剂、脱模剂、表面活性剂、蜡、防静电剂、染料、UV吸收剂、UV稳定剂或其他塑料添加剂。
  8. 根据权利要求1-7任一项所述的一种可生物降解聚酯组合物,其特征在于,所述可生物降解聚酯组合物在吹膜挤出速度为176Kg/h时,膜厚极差<0.2μm,膜厚相对偏差<1%。
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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105713356B (zh) 2016-03-07 2017-05-31 杨红梅 一种可生物降解聚酯组合物
CN105585825A (zh) 2016-03-07 2016-05-18 杨红梅 一种可生物降解聚酯组合物
EP3494169A1 (en) * 2016-08-02 2019-06-12 Vinventions USA, LLC Closure for a product-retaining container
CN107698944A (zh) * 2016-08-09 2018-02-16 营口永胜降解塑料有限公司 一种全生物降解覆盖地膜的生产工艺
CN107459783B (zh) * 2016-12-12 2018-07-27 金发科技股份有限公司 一种聚对苯二甲酸酯-共-癸二酸酯树脂组合物
CN108285622A (zh) * 2018-02-05 2018-07-17 东莞市鑫海环保材料有限公司 生物降解性材料及其制备方法
CN108276744A (zh) * 2018-02-05 2018-07-13 东莞市鑫海环保材料有限公司 一种新型生物降解材料薄膜及其制备方法
US20220034001A1 (en) * 2018-10-03 2022-02-03 Delstar Technologies, Inc. Polymer blend compositions and degradable extruded netting made therefrom
CN114269862A (zh) * 2019-06-13 2022-04-01 斯瓦蒙卢森堡公司 由聚合物共混物组合物制成的可降解挤出网
EP4136167A1 (en) * 2020-04-15 2023-02-22 3M Innovative Properties Company Compostable compositions, articles and methods of making compostable articles
CN112300547A (zh) * 2020-12-16 2021-02-02 洛阳绿之汇塑料降解科技有限公司 一种电器包装用全生物降解防静电膜及其制备方法
CN113583303A (zh) * 2021-07-28 2021-11-02 浙江晟祺实业有限公司 一种易降解包装材料及其制备方法
IT202100020990A1 (it) * 2021-08-03 2023-02-03 Maip S R L Rete biodegradabile
CN113754994A (zh) * 2021-09-14 2021-12-07 浙江晟祺实业有限公司 一种可降解材料及其制备方法
WO2023102683A1 (zh) * 2021-12-06 2023-06-15 万华化学集团股份有限公司 一种pbat树脂组合物及其制备方法和应用
CN114149664B (zh) * 2021-12-15 2023-07-14 中广核高新核材科技(苏州)有限公司 一种高挺度、强韧性全生物降解吹膜改性材料

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1726257A (zh) * 2002-10-22 2006-01-25 尤尼蒂卡株式会社 聚酯树脂水性分散体及其制备方法
WO2006026111A1 (en) * 2004-08-31 2006-03-09 3M Innovative Properties Company Aliphatic polyester resin compositions and shaped articles
CN101104702A (zh) * 2007-07-24 2008-01-16 陕西科技大学 不同结晶度脂肪族聚酯膜的制备工艺
CN101161701A (zh) * 2007-06-26 2008-04-16 广东雅图化工有限公司 一种作为汽车中涂漆的聚酯水分散体及其制备方法
CN101622311A (zh) 2007-03-01 2010-01-06 巴斯夫欧洲公司 含有生物柴油的聚酯混合物
CN102070880A (zh) * 2010-12-24 2011-05-25 金发科技股份有限公司 一种生物降解树脂组合物及其制品
CN102492271A (zh) * 2011-12-02 2012-06-13 金发科技股份有限公司 一种完全生物降解塑料材料及其制备方法
CN102639594A (zh) * 2009-11-05 2012-08-15 诺瓦蒙特股份公司 包含天然来源的聚合物和脂族-芳族共聚酯的生物可降解的组合物
CN105585826A (zh) * 2016-03-07 2016-05-18 金发科技股份有限公司 一种可生物降解聚酯组合物
CN105585827A (zh) * 2016-03-07 2016-05-18 金发科技股份有限公司 一种可生物降解聚酯组合物
CN105713356A (zh) * 2016-03-07 2016-06-29 杨红梅 一种可生物降解聚酯组合物

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954716A (en) 1971-09-08 1976-05-04 Bayer Aktiengesellschaft Process for the preparation of polyesters
BR9916117A (pt) * 1998-12-15 2001-09-04 Wolff Walsrode Ag Corpos moldados termoplásticos, biodegradáveis, exibindo uma estabilidade melhorada com respeito à hidrólise e uma resistência melhorada à rachadura por tensão
CA2399879A1 (en) 2000-02-22 2001-08-30 Alcoa Closure Systems International Inc. Lubricant combinations of erucamide and a saturated co-lubricant in compositions used for making closures
US6972315B2 (en) 2002-07-19 2005-12-06 Gross Richard A Enzyme-catalyzed polycondensations
CN1942527B (zh) * 2004-05-11 2010-12-01 花王株式会社 生物降解性树脂组合物
CN1284761C (zh) 2004-06-21 2006-11-15 沈阳工业大学 一种环戊酮的生产方法
ITMI20050452A1 (it) * 2005-03-18 2006-09-19 Novamont Spa Poliestere biodegradabile alifatico-aromatico
CN101864068B (zh) 2009-04-15 2012-03-07 中国石油天然气股份有限公司 一种聚对苯二甲酸丁二醇/己二酸丁二醇共聚酯的制备方法
EP2499189B1 (de) * 2009-11-09 2015-01-07 Basf Se Verfahren zur herstellung von schrumpffolien
CA2792699A1 (en) * 2010-03-24 2011-09-29 Basf Se Process for film production
US20110237750A1 (en) * 2010-03-24 2011-09-29 Basf Se Process for film production
US8686080B2 (en) * 2011-05-10 2014-04-01 Basf Se Biodegradable polyester film
EP2522695A1 (de) * 2011-05-10 2012-11-14 Basf Se Biologisch abbaubare Polyesterfolie
EP2551301A1 (de) * 2011-07-29 2013-01-30 Basf Se Biologisch abbaubare Polyesterfolie
US9096758B2 (en) * 2011-07-29 2015-08-04 Basf Se Biodegradable polyester foil
CN102863654B (zh) * 2012-10-11 2015-07-08 武汉华丽环保科技有限公司 一种淀粉和聚乳酸的复合材料及其制备方法
CN103044226B (zh) 2012-12-26 2014-09-03 淮安万邦香料工业有限公司 用己二酸制备环戊酮的方法
CN105195063B (zh) 2015-09-29 2017-10-27 山东国润生物医药有限公司 一种用于己二酸制备环戊酮的脱羧装置
CN105838039B (zh) * 2016-01-11 2018-05-01 珠海万通化工有限公司 一种pbat树脂组合物
CN105585824A (zh) 2016-03-07 2016-05-18 金发科技股份有限公司 一种可生物降解聚酯组合物
CN105585825A (zh) 2016-03-07 2016-05-18 杨红梅 一种可生物降解聚酯组合物

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1726257A (zh) * 2002-10-22 2006-01-25 尤尼蒂卡株式会社 聚酯树脂水性分散体及其制备方法
WO2006026111A1 (en) * 2004-08-31 2006-03-09 3M Innovative Properties Company Aliphatic polyester resin compositions and shaped articles
CN101622311A (zh) 2007-03-01 2010-01-06 巴斯夫欧洲公司 含有生物柴油的聚酯混合物
CN101161701A (zh) * 2007-06-26 2008-04-16 广东雅图化工有限公司 一种作为汽车中涂漆的聚酯水分散体及其制备方法
CN101104702A (zh) * 2007-07-24 2008-01-16 陕西科技大学 不同结晶度脂肪族聚酯膜的制备工艺
CN102639594A (zh) * 2009-11-05 2012-08-15 诺瓦蒙特股份公司 包含天然来源的聚合物和脂族-芳族共聚酯的生物可降解的组合物
CN102070880A (zh) * 2010-12-24 2011-05-25 金发科技股份有限公司 一种生物降解树脂组合物及其制品
CN102492271A (zh) * 2011-12-02 2012-06-13 金发科技股份有限公司 一种完全生物降解塑料材料及其制备方法
CN105585826A (zh) * 2016-03-07 2016-05-18 金发科技股份有限公司 一种可生物降解聚酯组合物
CN105585827A (zh) * 2016-03-07 2016-05-18 金发科技股份有限公司 一种可生物降解聚酯组合物
CN105713356A (zh) * 2016-03-07 2016-06-29 杨红梅 一种可生物降解聚酯组合物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3260494A4

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