WO2018157637A1 - 可生物降解聚合物组合物及其制备方法和应用 - Google Patents

可生物降解聚合物组合物及其制备方法和应用 Download PDF

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WO2018157637A1
WO2018157637A1 PCT/CN2017/113746 CN2017113746W WO2018157637A1 WO 2018157637 A1 WO2018157637 A1 WO 2018157637A1 CN 2017113746 W CN2017113746 W CN 2017113746W WO 2018157637 A1 WO2018157637 A1 WO 2018157637A1
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biodegradable polymer
weight
polymer composition
parts
temperature
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French (fr)
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卢昌利
蔡彤旻
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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金发科技股份有限公司
珠海万通化工有限公司
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Publication of WO2018157637A1 publication Critical patent/WO2018157637A1/zh

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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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • 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
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition

Definitions

  • the invention belongs to the technical field of polymer material modification, and particularly relates to a biodegradable polymer composition, a preparation method and application thereof.
  • 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.
  • the starch-based biodegradable polymer composition has the characteristics of high strength and good toughness and is widely used in film products.
  • the starch since the starch constitutes dispersibility, and the starch acts as a porous hydrophilic substance, when the environmental humidity changes, due to the adsorption of the starch and The water is released until it equilibrates with the ambient humidity at the interface, resulting in poor mechanical properties, particularly impact and tear properties.
  • Patent CN 1149261C prefers glycerol as a plasticizer while limiting the critical amount of plasticizer to from 2 to 8%, preferably from 3 to 7% by weight, based on the weight of the starch and thermoplastic polymer, obtained at 10 ° C and less than 5 A product with a high impact strength at % relative humidity.
  • the method effectively solves the brittleness problem of the starch-based biodegradable polymer composition under low temperature and low humidity conditions, but the disadvantage of the method is that glycerol is used as a high boiling plasticizer in environmental humidity.
  • Patent CN 1104467C uses a surfactant having a specific HLB value, and a composition of an aliphatic or aliphatic-aromatic copolyester having a ratio of viscosity average molecular weight to melt index (R) greater than 25,000 is used as a thermoplastic polymer.
  • a biodegradable multiphase composition that maintains high mechanical properties under conditions of low relative humidity.
  • the amount of surfactant used tends to be due to variations in the composition of the biodegradable multiphase composition system, resulting in insufficient or insufficient addition, resulting in non-uniform product properties.
  • the thermoplastic polymer selected in this patent is a polymer with a specific molecular weight and is not universal.
  • DSC Differential Scanning Calorimetry
  • a primary object of the present invention is to provide a biodegradable polymer composition which is biodegradable polymer combination
  • the material has excellent longitudinal and transverse tear properties under low temperature and low humidity conditions.
  • Another object of the present invention is to provide a process for the preparation of the above biodegradable polymer composition.
  • a biodegradable polymer composition comprising, by weight, parts by weight:
  • the differential scanning calorimeter DSC spectrum of the biodegradable polymer composition has a characteristic peak on the first heating curve, and the characteristic peak corresponds to a temperature T greater than 60 ° C, less than 95 ° C, preferably temperature T is greater than 65 ° C, less than 85 ° C, more preferably temperature T is greater than 70 ° C, less than 78 ° C.
  • the test condition of the DSC spectrum of the differential scanning calorimeter is: the sample amount of the biodegradable polymer composition is 5-10 mg, the nitrogen condition, the nitrogen purging speed is 20 ml/min, and the temperature rising range is 20 ° C to 240 ° C, The heating rate is 10 ° C / min, 240 ° C constant temperature 3 min, cooling to 20 ° C, cooling rate 10 ° C / min, and then heating to 240 ° C, heating rate 10 ° C / min.
  • the temperature T corresponding to the characteristic peak of the differential scanning calorimeter DSC spectrum on the first heating curve characterizes the plasticizing temperature of the starch phase in the biodegradable polymer composition, affecting the temperature T corresponding to the characteristic peak.
  • factors such as the structure or proportion of the raw material components, the change of the molecular weight of the polymer and the sequence structure of the molecular chain, the surface properties of the starch and the preparation process, etc., which will affect the finally prepared biodegradable polymer combination.
  • There is a big difference in the molecular structure of the object which results in a significant difference in the temperature T value corresponding to the characteristic peak.
  • the present invention has found through research that when the characteristic peak of the differential scanning calorimeter DSC spectrum of the biodegradable polymer composition on the first heating curve corresponds to a temperature T greater than 60 ° C and less than 95 ° C, the combination
  • the film obtained by the article has excellent longitudinal and transverse tear properties at 0 ° C and 10% humidity.
  • the temperature T corresponding to the characteristic peak is higher than 95 ° C or lower than 60 ° C, the tear property of the film is poor.
  • the biodegradable polymer composition in parts by weight, comprises the following components:
  • the biodegradable polymer composition in parts by weight, comprises the following components:
  • the flexible biodegradable polymer is selected from the group consisting of one or more of an aliphatic copolyester or an aliphatic-aromatic copolyester, preferably polybutylene adipate terephthalate (PBAT) a mixture of one or more of polycaprolactone (PCL) or polybutylene terephthalate (PBSeT).
  • PBAT polybutylene adipate terephthalate
  • PCL polycaprolactone
  • PBSeT polybutylene terephthalate
  • the surfactant is selected from one or more of a silane coupling agent, a titanate coupling agent or an aluminate coupling agent, and specific examples thereof include a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling.
  • the plasticizer is selected from the group consisting of water, glycerin, polyglycerin, ethoxylated polyglycerol, ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentane a mixture of one or more of a diol, sorbitol, sorbitol monoacetate, sorbitol diacetate, sorbitol monoethoxylate or sorbitol diethoxylate, preferably water, glycerol Or a mixture of one or more of polyglycerols.
  • a biodegradable polymer composition according to the present invention further comprises 0 to 20 parts by weight of polylactic acid, 0 to 20 parts by weight of an organic or inorganic filler, and 0 to parts by weight. 4 parts by weight of at least one of the other auxiliaries described below: release agents, dyes or other plastic additives.
  • the organic filler is selected from one or a mixture of natural fibers, straw, and wood flour;
  • 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. a mixture of one or more of salt, mica, fiberglass or mineral fibers.
  • the release agent is: one of silicone oil, paraffin wax, white mineral oil, petrolatum or a mixture of two or more;
  • the dye is one of carbon black, black species, titanium dioxide, zinc sulfide, indigo blue, fluorescent orange or a mixture of two or more;
  • the other plastic additives are: antioxidants, lubricants, and the like.
  • Suitable antioxidants are selected from one or more of a hindered amine antioxidant, a hindered phenol antioxidant or a phosphite antioxidant, and specifically may be listed as 1010, 168, 1076, 445, 1098.
  • a suitable lubricant is a polymer complex ester selected from the group consisting of stearic acid amide, oleic acid amide, erucic acid amide, zinc stearate, metal soap, ethylene bis stearamide, One or a mixture of two or more of a polyethylene wax and a silicone lubricant.
  • the invention also provides a preparation method of the above biodegradable polymer composition, comprising the following steps:
  • the starch is added to the surfactant aqueous solution, stirring reaction for 2 ⁇ 5h, spray-dried to obtain surfactant-modified starch;
  • step b the temperature of the air inlet of the spray drying is 140 ° C - 200 ° C, the temperature of the air outlet is 70 ° C - 130 ° C, and the rotational speed is 2000 rpm - 3000 rpm.
  • the present invention also provides a biodegradable polymer composition as described above for preparing a shopping bag, a compost bag, a mulch film, a protective cover film, a silo film, a film tape, a fabric, a non-woven fabric, a textile, a fishing net, a load-bearing bag or The application in the garbage bag.
  • the invention has the following beneficial effects:
  • the present invention investigates the unexpected discovery that a biodegradable polymer composition with a flexible biodegradable polymer as a continuous phase and a starch as a dispersed phase, a differential scanning calorimeter of the biodegradable polymer composition
  • the temperature peak corresponding to the characteristic peak of the DSC spectrum on the first heating curve is greater than 60 ° C.
  • the film obtained from the composition has excellent cross-section at 0 ° C and 10% humidity. To the tear performance.
  • Example 1 is a DSC chart of the biodegradable polymer composition of Example 1.
  • the materials used in the present invention are as follows, but are not limited to these materials:
  • silane coupling agent KH560 from the market;
  • Plasticizers water, glycerin, polyglycerol, all from the market;
  • T g glass transition temperature
  • the glassy transition temperature ( Tg ) of the flexible biodegradable polymer was tested on a differential scanning calorimeter model NETZSCH DSC 204F1.
  • test conditions were as follows: sample amount 5-10 mg, temperature rise range -80 ° C to 250 ° C, 250 ° C constant temperature 3 min, rise/fall rate 10 ° C / min, nitrogen conditions, nitrogen purge rate 20 ml / min, 1.5 cycles.
  • the temperature (T) corresponding to the characteristic peak of the biodegradable polymer composition was tested on a differential scanning calorimeter model NETZSCH DSC 204F1.
  • the test conditions are as follows: the sample amount of the biodegradable polymer composition is 5-10 mg, the nitrogen condition, the nitrogen purging speed is 20 ml/min, the temperature rising range is 20 ° C to 240 ° C, the heating rate is 10 ° C / min, the temperature is 240 ° C for 3 min, and the temperature is lowered to 20 ° C, the cooling rate of 10 ° C / min, and then to 240 ° C, the heating rate of 10 ° C / min, the characteristic peak is a characteristic peak of the DSC spectrum on the first heating curve.
  • the curve of number [1.1] is the first temperature rise curve
  • the curve of number [1.3] is the first temperature drop curve
  • the curve of number [1.5] is the second temperature rise curve
  • the temperature T is the temperature on the first temperature rise curve.
  • the film test sample made of the cut biodegradable polymer composition having a film thickness of 15 ⁇ m was placed in a refrigerator at 0 ° C, and left to stand for 2 h, according to GB T/16578.2-2009, under 10% humidity conditions. Test the longitudinal and transverse tear properties of the film samples.
  • the surfactant is added to the aqueous solution to prepare a 0.5% by mass aqueous surfactant solution;
  • Example 1 In step b, the stirring reaction time was 2 h, the spray drying air inlet temperature was 150 ° C, the air outlet temperature was 90 ° C, and the rotation speed was 2200 rpm.
  • Example 3 In step b, the stirring reaction time was 4 h, the spray drying air inlet temperature was 160 ° C, the air outlet temperature was 100 ° C, and the rotation speed was 2500 rpm; the rest was the same as in Example 1.
  • Example 6 In step b, the stirring reaction time was 5 h, the spray drying air inlet temperature was 180 ° C, the air outlet temperature was 95 ° C, and the rotation speed was 2800 rpm; the rest was the same as in Example 1.
  • Example 7 Substituting PCL with PBSeT, in step b, the stirring reaction time was 3 h, the spray drying air inlet temperature was 170 ° C, the air outlet temperature was 110 ° C, and the rotation speed was 2700 rpm; the rest was the same as in Example 3.
  • Example 8 PBAT was used instead of PCL.
  • the stirring reaction time was 5 h
  • the spray dried air inlet temperature was 165 ° C
  • the air outlet temperature was 105 ° C
  • the rotational speed was 2300 rpm; the rest was the same as in Example 3.
  • Comparative Example 1 Surfactant was first added to an aqueous solution to prepare a 0.5% by mass aqueous surfactant solution; then starch (N-starch), aqueous surfactant solution, biodegradable polymer, plasticized After the mixture was uniformly mixed, it was put into a twin-screw extruder, extruded at 140 ° C - 180 ° C, and granulated to obtain a biodegradable polymer composition.
  • Comparative Example 2 According to the formulation of Table 1, the rest of the process was the same as the example.
  • the differential scanning calorimeter DSC spectrum of the biodegradable polymer composition in the examples has a characteristic peak corresponding to the temperature T on the first heating curve corresponding to a temperature T greater than 60 ° C, less than 95.
  • the film obtained from the composition has excellent longitudinal and transverse tearing properties at 0 ° C and 10% humidity; in the comparative example, when the temperature T corresponding to the characteristic peak is higher than 95 ° C, The film obtained by the composition had poor longitudinal and transverse tear properties at 0 ° C and 10% humidity.

Abstract

一种可生物降解聚合物组合物及其制备方法和应用，包括如下组分：ⅰ、5-95重量份的至少一种玻璃化转变温度低于-20℃的柔性可生物降解聚合物作为连续相；ⅱ、3-75重量份的淀粉作为分散相；ⅲ、0.5-10重量份的表面活性剂；ⅳ、2-20重量份的增塑剂。当所述可生物降解聚合物组合物的差示扫描量热仪DSC谱图在第一次升温曲线上的特征峰对应的温度T大于60℃，小于95℃时，由该组合物所制得的膜材在0℃和10%湿度条件下具有优异的纵横向撕裂性能。所述生物降解聚合物组合物能用于制备各种袋或膜制品。

Description

一种可生物降解聚合物组合物及其制备方法和应用 技术领域
本发明属于高分子材料改性技术领域，具体涉及一种可生物降解聚合物组合物及其制备方法和应用。
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。
基于淀粉的可生物降解聚合物组合物具有强度高、韧性好的特点，广泛应用于薄膜产品。但基于淀粉的可生物降解聚合物组合物所制成的制品中，由于淀粉构成了分散性，且淀粉作为一种多孔性的亲水性物质，在环境湿度发生变化时，由于淀粉的吸附和释放水，直至它在界面上与环境湿度达成平衡，导致制品的机械性能，特别是冲击性能和撕裂性能变差。
为了解决基于淀粉的可生物降解聚合物在相对低湿度的环境下，材料倾向变脆的问题。专利CN 1149261C优选丙三醇作为增塑剂，同时将增塑剂的临界数量限定为淀粉和热塑性聚合物重量的2-8％，优选3-7重量％，获得了具有在10℃和小于5％相对湿度下，具有较高冲击强度的产品。该方法有效解决了基于淀粉的可生物降解聚合物组合物在低温低湿条件下的脆性问题，但该方法的不足之处在于，丙三醇作为一种高沸点的增塑剂，在环境湿度发生周期性变化时，由于通风气流的作用或其它亲水性材料如纤维素的接触会发生迁移，导致大多数丙三醇易于从体系中丧失，从而导致制品在存储过程中易发生性能的衰减，影响了制品的使用寿命。
专利CN 1104467C采用具有特定HLB值的界面活性剂，同时选用粘均分子量与熔体指数之比(R)大于25000的脂族或脂族-芳族共聚酯的组合物作为热塑性聚合物，制备了在相对湿度低的条件下仍能保持高机械性能的可生物降解多相组合物。但界面活性剂的使用量往往会由于可生物降解多相组合物体系组分的变化，出现添加不足或添加过量的偏差，造成制品性能不均一。同时，该专利中选用的热塑性聚合物是具有特定分子量的聚合物，不具备普遍性。
差示扫描量热分析(DSC)是最常用的热分析仪器之一，用于表征聚合物熔融结晶过程，反应了分子链结构与结晶之间的关系，分子链结构的变化，直接决定了DSC在升温或降温的过程中熔融或结晶行为。本发明通过研究意外的发现，以至少一种玻璃化转变温度低 于-20℃的柔性可生物降解聚合物作为连续相，同时以表面改性预处理后的淀粉作为分散相的可生物降解聚合物组合物，当该可生物降解聚合物组合物的差示扫描量热仪DSC谱图在第一次升温曲线上的特征峰值对应的温度T大于60℃，小于95℃时，由该组合物所制得的膜材在低温低湿条件下具有优异的纵横向撕裂性能。
发明内容
本发明的首要目的在于提供一种可生物降解聚合物组合物，该可生物降解聚合物组合
物在低温低湿条件下具有优异的纵横向撕裂性能。
本发明的另一目的在于提供上述可生物降解聚合物组合物的制备方法。
本发明是通过以下技术方案实现的：
一种可生物降解聚合物组合物，按重量份数计，包括如下组分:
i、5-95重量份的至少一种玻璃化转变温度低于-20℃的柔性可生物降解聚合物作为连续相；
ii、3-75重量份的淀粉作为分散相；
iii、0.5-10重量份的表面活性剂；
iv、2-20重量份的增塑剂，
其中，所述可生物降解聚合物组合物的差示扫描量热仪DSC谱图在第一次升温曲线上存在一个特征峰，该特征峰值对应的温度T大于60℃，小于95℃，优选温度T大于65℃，小于85℃，更优选温度T大于70℃，小于78℃。
其中，所述差示扫描量热仪DSC谱图的测试条件为：可生物降解聚合物组合物样品量5～10mg，氮气条件，氮气吹扫速度20ml/min，升温范围20℃～240℃，升温速率10℃/min，240℃恒温3min，降温至20℃，降温速率10℃/min，再升温至240℃，升温速率10℃/min。
差示扫描量热仪DSC谱图在第一次升温曲线上的特征峰值对应的温度T表征的是可生物降解聚合物组合物中淀粉相的塑化温度，影响该特征峰值对应的温度T的因素有很多，比如原料组分的结构或比例的不同，聚合物分子量和分子链序列结构的变化，淀粉的表面性能及制备工艺过程等诸多因素，都会影响最终制备得到的可生物降解聚合物组合物的分子结构存在较大区别，从而导致其特征峰值对应的温度T值存在明显差异。
本发明通过研究发现，当可生物降解聚合物组合物的差示扫描量热仪DSC谱图在第一次升温曲线上的特征峰值对应的温度T大于60℃，小于95℃时，由该组合物所制得的膜材在0℃和10％湿度条件下具有优异的纵横向撕裂性能。当该特征峰值对应的温度T高于95℃或低于60℃时，膜材的撕裂性能较差。
优选的，所述的一种可生物降解聚合物组合物，按重量份数计，包括如下组分:
i、30-85重量份的至少一种玻璃化转变温度低于-30℃的柔性可生物降解聚合物作为连续相；
ii、10-50重量份的淀粉作为分散相；
iii、1-8重量份的表面活性剂；
iv、5-15重量份的增塑剂。
更优选的，所述的一种可生物降解聚合物组合物，按重量份数计，包括如下组分:
i、50-78重量份的至少一种玻璃化转变温度低于-40℃的柔性可生物降解聚合物作为连续相；
ii、15-38重量份的淀粉作为分散相；
iii、2-5重量份的表面活性剂；
iv、7-12重量份的增塑剂。
所述柔性可生物降解聚合物选自脂肪族共聚酯或脂肪族-芳香族共聚酯中的一种或几种的混合，优选为聚己二酸对苯二甲酸丁二醇酯(PBAT)、聚己内酯(PCL)或聚癸二酸对苯二甲酸丁二醇酯(PBSeT)中的一种或几种的混合。
所述表面活性剂选自硅烷偶联剂、钛酸酯偶联剂或铝酸酯偶联剂中的一种或几种，具体例子如硅烷偶联剂KH550、硅烷偶联剂KH560、硅烷偶联剂KH570、钛酸酯偶联剂KR-TTS、钛酸酯偶联剂KR-38S、钛酸酯偶联剂KR-12、铝酸酯偶联剂DL-411-A等。
所述增塑剂选自水、甘油、聚甘油、乙氧基聚甘油、乙二醇、聚乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇，戊二醇、山梨醇、山梨醇一单乙酸酯、山梨醇二乙酸酯、山梨醇单乙氧基化物或山梨醇二乙氧基化物中的一种或几种的混合，优选水、甘油或聚甘油中的一种或几种的混合。
根据实际性能需要，本发明所述的一种可生物降解聚合物组合物，按重量份数计，还包括0至20重量份的聚乳酸、0至20重量份的有机或无机填料、0至4重量份的至少一种下述其他助剂：脱模剂、染料或其他塑料添加剂。
所述有机填料选自天然纤维、秸秆、木粉中的一种或几种的混合；
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几种的混合。
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；
所述其他塑料添加剂为：抗氧剂、润滑剂等。
合适的抗氧剂选自受阻胺类抗氧剂、受阻酚类抗氧剂或亚磷酸酯类抗氧剂中的一种或几种，具体可以列举出1010、168、1076、445、1098中的一种或者两种及以上的混合物；合适的润滑剂为选自硬酯酰胺、油酸酰胺、芥酸酰胺、硬脂酸锌、金属皂的高分子复合酯、乙撑双硬脂酰胺、聚乙烯蜡、硅酮类润滑剂中的一种或两种以上的混合物。
本发明还提供了上述一种可生物降解聚合物组合物的制备方法，包括如下步骤：
a、将表面活性剂加入水溶液中，制备得到质量百分浓度为0.1-10％的表面活性剂水溶液；
b、按比例在搅拌的条件下，将淀粉加入表面活性剂水溶液中，搅拌反应2～5h，经喷雾干燥得到经表面活性剂改性淀粉；
c、将经表面活性剂改性淀粉、可生物降解聚合物、增塑剂、有机或无机填料、聚乳酸、其他助剂混合均匀后，投入双螺杆挤出机中，于140℃-180℃挤出、造粒，得到可生物降解聚合物组合物。
其中，步骤b中，喷雾干燥的进风口温度为140℃-200℃，出风口温度为70℃-130℃，转速为2000rpm-3000rpm。
本发明还提供了上述的一种可生物降解聚合物组合物在制备购物袋、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、承重袋或垃圾袋中的应用。
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，以柔性可生物降解聚合物作为连续相，同时以淀粉作为分散相的可生物降解聚合物组合物，当该可生物降解聚合物组合物的差示扫描量热仪DSC谱图在第一次升温曲线上存在的特征峰值对应的温度T大于60℃，小于95℃时，由该组合物所制得的膜材在0℃和10％湿度条件下具有优异的纵横向撕裂性能。
附图说明
图1为实施例1的可生物降解聚合物组合物的DSC谱图。
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如下，但不仅限于这些原料：
PBAT，Tg＝-25℃～-29℃，金发科技股份有限公司；
PBSeT，Tg＝-32℃～-38℃，金发科技股份有限公司；
PCL，Tg＝-58℃～-63℃，美国苏威塑料有限公司；
PPC，Tg＝32℃～46℃，南通龙达生物新材料科技有限公司；
PLA，NatureWorks；
淀粉(N-starch)，山东寿光巨能金玉米开发有限公司；
表面活性剂：硅烷偶联剂KH560，来源于市购；
增塑剂：水、甘油、聚甘油，均来源于市购；
性能测试方法：
柔性可生物降解聚合物玻璃化转变温度(Tg)的测试
在型号为NETZSCH DSC 204F1的差示扫描量热仪上测试柔性可生物降解聚合物玻璃化转变温度(Tg)。
测试条件为：样品量5～10mg，升温范围-80℃～250℃，250℃恒温3min，升/降温速率10℃/min，氮气条件，氮气吹扫速度20ml/min，1.5个循环。
可生物降解聚合物组合物特征峰值对应的温度(T)的测试
在型号为NETZSCH DSC 204F1的差示扫描量热仪上测试可生物降解聚合物组合物的特征峰值对应的温度(T)。
测试条件为：可生物降解聚合物组合物样品量5～10mg，氮气条件，氮气吹扫速度20ml/min，升温范围20℃～240℃，升温速率10℃/min，240℃恒温3min，降温至20℃，降温速率10℃/min，再升温至240℃，升温速率10℃/min，特征峰值是DSC谱图在第一次升温曲线上存在的一个特征峰值。如图1所示，其中，编号[1.1]的曲线为第一次升温曲线；编号[1.3]的曲线为第一次降温曲线；编号[1.5]的曲线为第二次升温曲线；特征峰值对应的温度T为第一次升温曲线上的温度。
可生物降解聚合物组合物薄膜纵横向撕裂性能的测试
将裁制好的可生物降解聚合物组合物制成的膜厚为15μm的薄膜测试样品置于0℃的冰箱中，冷却放置2h，按照GB T/16578.2—2009，在10％的湿度条件下，测试薄膜样品的纵横向撕裂性能。
实施例1-11：可生物降解聚合物组合物的制备
a、将表面活性剂加入水溶液中，制备得到质量百分浓度为0.5％的表面活性剂水溶液；
b、按表1配方，在搅拌的条件下，将淀粉(N-starch)加入表面活性剂水溶液中，搅拌反应2～5h，经喷雾干燥得到经表面活性剂改性淀粉(M-starch)，喷雾干燥的进风口温度为140℃-200℃，出风口温度为70℃-130℃，转速为2000rpm-3000rpm；
c、将经表面活性剂改性淀粉(M-starch)、可生物降解聚合物、增塑剂、聚乳酸混合均匀后， 投入双螺杆挤出机中，于140℃-180℃挤出、造粒，得到可生物降解聚合物组合物。
其中：
实施例1：步骤b中，搅拌反应的时间为2h，喷雾干燥的进风口温度为150℃，出风口温度为90℃，转速为2200rpm；。
实施例3：步骤b中，搅拌反应的时间为4h，喷雾干燥的进风口温度为160℃，出风口温度为100℃，转速为2500rpm；其余同实施例1。
实施例6：步骤b中，搅拌反应的时间为5h，喷雾干燥的进风口温度为180℃，出风口温度为95℃，转速为2800rpm；其余同实施例1。
实施例7：用PBSeT替代PCL，步骤b中，搅拌反应的时间为3h，喷雾干燥的进风口温度为170℃，出风口温度为110℃，转速为2700rpm；其余同实施例3。
实施例8：用PBAT替代PCL，步骤b中，搅拌反应的时间为5h，喷雾干燥的进风口温度为165℃，出风口温度为105℃，转速为2300rpm；其余同实施例3。
对比例1：先将表面活性剂加入水溶液中，制备得到质量百分浓度为0.5％的表面活性剂水溶液；再将淀粉(N-starch)、表面活性剂水溶液、可生物降解聚合物、增塑剂混合均匀后，投入双螺杆挤出机中，于140℃-180℃挤出、造粒，得到可生物降解聚合物组合物。
对比例2：按表1配方，其余工艺同实施例。
表1实施例1-11及对比例1-2的性能测试结果(重量份)
Figure PCTCN2017113746-appb-000001
由表1结果可以看出，实施例中当可生物降解聚合物组合物的差示扫描量热仪DSC谱图在第一次升温曲线上存在的特征峰值对应的温度T大于60℃，小于95℃时，由该组合物所制得的膜材在0℃和10％湿度条件下具有优异的纵横向撕裂性能；对比例中当该特征峰值对应的温度T高于95℃时，由该组合物所制得的膜材在0℃和10％湿度条件下的纵横向撕裂性能较差。

Claims (12)

  1. 一种可生物降解聚合物组合物，其特征在于，按重量份数计，包括如下组分:
    i、5-95重量份的至少一种玻璃化转变温度低于-20℃的柔性可生物降解聚合物作为连续相；
    ii、3-75重量份的淀粉作为分散相；
    iii、0.5-10重量份的表面活性剂；
    iv、2-20重量份的增塑剂，
    其中，所述可生物降解聚合物组合物的差示扫描量热仪DSC谱图在第一次升温曲线上存在一个特征峰，该特征峰值对应的温度T大于60℃，小于95℃，优选温度T大于65℃，小于85℃，更优选温度T大于70℃，小于78℃。
  2. 根据权利要求1所述的一种可生物降解聚合物组合物，其特征在于，所述差示扫描量热仪DSC谱图的测试条件为：可生物降解聚合物组合物样品量5～10mg，氮气条件，氮气吹扫速度20ml/min，升温范围20℃～240℃，升温速率10℃/min，240℃恒温3min，降温至20℃，降温速率10℃/min，再升温至240℃，升温速率10℃/min。
  3. 根据权利要求1所述的一种可生物降解聚合物组合物，其特征在于，按重量份数计，包括如下组分:
    i、30-85重量份的至少一种玻璃化转变温度低于-30℃的柔性可生物降解聚合物作为连续相；
    ii、10-50重量份的淀粉作为分散相；
    iii、1-8重量份的表面活性剂；
    iv、5-15重量份的增塑剂。
  4. 根据权利要求3所述的一种可生物降解聚合物组合物，其特征在于，按重量份数计，包括如下组分:
    i、50-78重量份的至少一种玻璃化转变温度低于-40℃的柔性可生物降解聚合物作为连续相；
    ii、15-38重量份的淀粉作为分散相；
    iii、2-5重量份的表面活性剂；
    iv、7-12重量份的增塑剂。
  5. 根据权利要求1-4任一项所述的一种可生物降解聚合物组合物，其特征在于，所述柔性可生物降解聚合物选自脂肪族共聚酯或脂肪族-芳香族共聚酯中的一种或几种的混合，优选聚己二酸对苯二甲酸丁二醇酯、聚己内酯或聚癸二酸对苯二甲酸丁二醇酯中的一种或几种的混合。
  6. 根据权利要求1-4任一项所述的一种可生物降解聚合物组合物，其特征在于，所述表面活性剂选自硅烷偶联剂、钛酸酯偶联剂或铝酸酯偶联剂中的一种或几种。
  7. 根据权利要求1-4任一项所述的一种可生物降解聚合物组合物，其特征在于，所述增塑剂选自水、甘油、聚甘油、乙氧基聚甘油、乙二醇、聚乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、戊二醇、山梨醇、山梨醇一单乙酸酯、山梨醇二乙酸酯、山梨醇单乙氧基化物或山梨醇二乙氧基化物中的一种或几种的混合，优选水、甘油或聚甘油中的一种或几种的混合。
  8. 根据权利要求1-4任一项所述的一种可生物降解聚合物组合物，其特征在于，按重量份数计，所述可生物降解聚合物组合物还包括0至20重量份的聚乳酸、0至20重量份的有机或无机填料、0至4重量份的至少一种下述其他助剂：脱模剂、染料或其他塑料添加剂。
  9. 根据权利要求8所述的一种可生物降解聚合物组合物，其特征在于，所述有机填料选自天然纤维、秸秆、木粉中的一种或几种的混合；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几种的混合。
  10. 根据权利要求1-9任一项所述的一种可生物降解聚合物组合物的制备方法，其特征在于，包括如下步骤：
    a、将表面活性剂加入水溶液中，制备得到质量百分浓度为0.1-10％的表面活性剂水溶液；
    b、按比例在搅拌的条件下，将淀粉加入表面活性剂水溶液中，搅拌反应2～5h，经喷雾干燥得到经表面活性剂改性淀粉；
    c、将经表面活性剂改性淀粉、可生物降解聚合物、增塑剂、聚乳酸、有机或无机填料、其他助剂混合均匀后，投入双螺杆挤出机中，于140℃-180℃挤出、造粒，得到可生物降解聚合物组合物。
  11. 根据权利要求10所述的一种可生物降解聚合物组合物的制备方法，其特征在于，步骤b中，喷雾干燥的进风口温度为140℃-200℃，出风口温度为70℃-130℃，转速为2000rpm-3000rpm。
  12. 根据权利要求1-9任一项所述的一种可生物降解聚合物组合物在制备购物袋、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、承重袋或垃圾袋中的应用。
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