WO2022000465A1 - 多级改性的热塑性淀粉母粒及其在制备淀粉基生物降解薄膜中的应用 - Google Patents
多级改性的热塑性淀粉母粒及其在制备淀粉基生物降解薄膜中的应用 Download PDFInfo
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- WO2022000465A1 WO2022000465A1 PCT/CN2020/100123 CN2020100123W WO2022000465A1 WO 2022000465 A1 WO2022000465 A1 WO 2022000465A1 CN 2020100123 W CN2020100123 W CN 2020100123W WO 2022000465 A1 WO2022000465 A1 WO 2022000465A1
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- WIPO (PCT)
- Prior art keywords
- starch
- time
- speed stirring
- speed
- thermoplastic starch
- Prior art date
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- 229920002472 Starch Polymers 0.000 title claims abstract description 76
- 235000019698 starch Nutrition 0.000 title claims abstract description 76
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- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 claims description 29
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 26
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- 238000000034 method Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
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- 240000003183 Manihot esculenta Species 0.000 description 1
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Definitions
- the invention relates to a multi-stage modified thermoplastic starch master batch, a preparation method thereof, its application in preparing a starch-based biodegradable film, and the prepared starch-based biodegradable film, belonging to the field of biodegradable plastics.
- Biodegradable plastics are polymeric materials that can decompose into carbon dioxide and water in a relatively short period of time under normal environmental conditions.
- the common ones are: biodegradable homopolyester, such as PHA, PLA, PHB, PCL, PHBV, etc.; biodegradable copolyester, such as PBS, PBSA, etc.; natural products with polysaccharide structure, such as thermoplastic starch resin (TPS), Cellulose acetate, etc.
- TPS thermoplastic starch resin
- Thermoplastic starch refers to that starch is modified by steps such as esterification and grafting.
- Thermoplastic starch is inexpensive and fully degradable, making it the material of choice for biodegradable plastics.
- the biodegradable films made of common thermoplastic starch have disadvantages such as relatively poor mechanical properties, rough film surface, and poor transparency.
- the compatibility of starch with other biodegradable materials is poor, and the amount of starch added is relatively limited.
- the increase of starch content has a great influence on mechanical properties and film blowing efficiency.
- the method can mainly increase the starch content in the biodegradable film, and the prepared film maintains good mechanical properties, film surface smoothness and certain transparency.
- the purpose of the present invention is to provide a kind of multi-stage modified thermoplastic starch masterbatch, which can effectively improve the compatibility of starch with other biodegradable materials, increase the starch content in the biodegradable film at the same time, and maintain good mechanical properties and film. Surface finish and some transparency.
- thermoplastic starch masterbatch is prepared from the following raw materials by weight:
- the starch is subjected to a four-stage classification modification treatment, and the classification modification treatment is as follows: take 100 parts of starch with a moisture content of 15-30%, and stir it at a high speed in a high-speed mixer for the first time at room temperature. ; Heat up to 50-70°C, add polybutadiene, plasticizer and chemical modifier, and stir at high speed for the second time; then heat up to 75-95°C, add tackifier, lubricant, filler, chain extension Add the biodegradable resin for master batch at this temperature, and stir at high speed for the fourth time; stop stirring, and add twin-screw extruder to melt and extrude after holding for a period of time.
- the classification modification treatment is as follows: take 100 parts of starch with a moisture content of 15-30%, and stir it at a high speed in a high-speed mixer for the first time at room temperature. ; Heat up to 50-70°C, add polybutadiene, plasticizer and chemical modifier, and stir at high
- the plasticizer is one or more of glycerol, sorbitol, and epoxidized soybean oil;
- the polybutadiene is hydroxyl-terminated polybutadiene, epoxidized polybutadiene, 1,2- One or more of polybutadiene homopolymer;
- chemical modifier is one or more of maleic anhydride, citric acid, glycidyl methacrylate;
- tackifier is polyvinyl acetate, One or both of the ethylene-ethyl acrylate copolymer,
- the lubricant is one or more of calcium stearate, oleic acid amide, erucic acid amide;
- the filler is talc, calcium carbonate, barium sulfate, One or more of montmorillonite and mica powder;
- the chain extender is a mixture of one or more of isocyanate chain extenders, epoxy chain extenders and oxazoline chain extenders.
- modified starch Preferably, 1-10 parts of modified starch are also included, and the modified starch is one or both of oxidized starch and hydroxypropyl starch.
- the polybutadiene is a mixture of hydroxyl-terminated polybutadiene and epoxidized polybutadiene, wherein the ratio of hydroxyl-terminated polybutadiene to epoxidized polybutadiene is 3:1-1 :1wt.
- the tackifier is polyvinyl acetate and ethylene-ethyl acrylate copolymer, and the mixing ratio of polyvinyl acetate and ethylene-ethyl acrylate copolymer is 3:1-1:1wt.
- the biodegradable resin for the master batch is one or both of PBAT and PBSA.
- succinic acid accounts for 30-45% of the copolymerization ratio
- adipic acid accounts for 15-30% of the copolymerization ratio
- butanediol accounts for 40-55% of the copolymerization ratio.
- the first high-speed stirring speed is 600-1000 rpm for 1-5 minutes
- the second, third and fourth high-speed stirring speeds are all 800-1200 rpm
- the second time is 800-1200 rpm.
- the high-speed stirring time is 5-20 minutes
- the third high-speed stirring time is 5-15 minutes
- the fourth high-speed stirring time is 1-5 minutes
- the holding time is 2-12 hours.
- thermoplastic starch master batch its step comprises:
- thermoplastic starch masterbatch The heat-insulated starch mixture is added to a twin-screw extruder, extruded, air-cooled, and pelletized to make thermoplastic starch masterbatch.
- the first high-speed stirring speed is 600-1000 rpm for 1-5 minutes
- the second, third and fourth high-speed stirring speeds are all 800-1200 rpm
- the second time is 800-1200 rpm.
- the high-speed stirring time is 5-20 minutes
- the third high-speed stirring time is 5-15 minutes
- the fourth high-speed stirring time is 1-5 minutes
- the holding time is 2-12 hours.
- a twin-screw extruder is used for melt extrusion, the length-diameter ratio of the twin-screw extruder is 44:1-60:1, the temperature range is 110-160°C, and the screw speed is 150-600rpm , the end of the extruder has a vacuum exhaust function module.
- modified starch Preferably, 1-10 parts of modified starch are also added in step (1), and the modified starch is one or both of oxidized starch and hydroxypropyl starch.
- thermoplastic starch masterbatch in the preparation of starch-based biodegradable films.
- a starch-based biodegradable film is characterized in that: it is prepared from the following raw materials by weight:
- thermoplastic starch masterbatch 40-80 parts of above-mentioned thermoplastic starch masterbatch
- Biodegradable resin 40-55 parts 40-55 parts.
- the biodegradable resin is one or a mixture of PLA, PBSA, PBAT, and PPC.
- thermoplastic starch masterbatch is blended with the biodegradable resin, and blow-molded to obtain the starch-based biodegradable film.
- the film blowing temperature is 145-175°C, and the blowing ratio is 3:1-5.5:1.
- thermoplastic starch masterbatch is first subjected to four-stage modification treatment by using a high-mixer, and the first stage is to mix native starch and modified starch at room temperature.
- the addition of modified starch is beneficial to the reduction of gelatinization temperature, and at the same time improves gelatinization stability and compatibility with other biodegradable materials;
- second The temperature is gradually raised to 50-70 ° C, a part of the auxiliary agent is added, and the second high-speed stirring is performed.
- the compounding of plasticizers such as a fixed ratio of glycerol and sorbitol or glycerol and epoxidized soybean oil, can play a more efficient plasticizing effect; the compatibility of polybutadiene with starch and PBSA matrix is relatively high. Poor, the micro-nano polybutadiene particles formed by mixing a trace amount of polybutadiene into the plasticizer can form a topological network structure with the modified starch and modified PBSA added later through coupling, partial hydrogen bonding and chemical interaction. , on the one hand, it can reduce the entanglement of the matrix polymer chains. When the final material is subjected to tensile force, the micro-nano particles are soft and deformed at first.
- this topology due to the existence of this topology near the particle, as the stretching continues, it will generate The phenomenon of micropores and stretching necks, but at the same time, these micropores are relatively resistant to stretching and absorb more energy due to the existence of topology;
- the orientation of the chains in the stretching direction is more conducive to inducing crystallization, and the final material can obtain higher strength, toughness and moderate elongation at break.
- the key point is that the incompatible polybutadiene can produce micro-nano dispersion, and at the same time have a suitable interaction with modified starch, modified PBSA, etc., the interaction is too strong and too Weak are not conducive to obtaining this topology.
- thermoplastic starch have a certain reactivity, and can generate a certain interaction force with polybutadiene, and can also promote its compatibility with other degradable materials.
- three chemical modifiers, maleic anhydride, citric acid, and glycidyl methacrylate were added to graft starch, and PBSA was modified at the same time.
- the modified starch and modified PBSA interacted with polybutadiene micro-nano particles, further To promote the formation of the topology, the grafting reaction partially occurs during the 4-stage mixing process, but mainly occurs during the twin-screw melt extrusion process.
- auxiliaries are not added here to make the chemical modifier react better with starch and avoid the chemical modifier and other auxiliaries to react; agent, lubricant, filler, chain extender) for the third high-speed stirring, under this condition, the mixing ratio of tackifier (polyvinyl acetate and ethylene-ethyl acrylate copolymer is 1:1-3:
- the addition of 1wt) on the one hand improves the dispersion stability of various powder mixing (because the tackifier has been partially softened), on the other hand, it can also improve the compatibility of different phases in the later melt extrusion process. During the process, it can improve melt strength, improve bubble stability during blow molding, and maintain higher transparency and gloss.
- lubricants one or more of calcium stearate, oleic acid amide, and erucic acid amide
- lubricants one or more of calcium stearate, oleic acid amide, and erucic acid amide
- Fillers one or more of talc, calcium carbonate, barium sulfate, montmorillonite, mica powder
- chain extenders can improve the compatibility of starch and biodegradable resins through reactive compatibilization in the later extrusion and film blowing process, and can also improve the stability of biodegradable materials and blown film bubbles.
- biodegradable resin for masterbatch one or both of PBAT and PBSA
- the previous additives are all powder or liquid, which can be better miscible with each other, biodegradable
- the degradable resin is in the form of particles, and it is relatively easy to mix when added alone at the end.
- these biodegradable resins added can also generate partial esters with chemically modified starch (such as maleic anhydride modified starch) in the next stage of melt extrusion. Exchange reactions, which in turn will improve the compatibility of thermoplastic starch masterbatches with other biodegradable resins during the blow molding stage.
- the modified thermoplastic starch not only has much better performance than conventional thermoplastic starch, but also has greatly improved compatibility with other biodegradable materials, thereby increasing the starch content in the biodegradable film and maintaining good mechanical properties, The surface smoothness and certain transparency of the film will also greatly reduce the cost of the biodegradable film and improve the biodegradability of the film.
- Epoxy chain extender The structural formula that can be used is as follows:
- KL-E4370 is used in the embodiment of the present invention, the product of Shanxi Chemical Research Institute.
- Oxazoline chain extender the structural formula that can be used is as follows:
- B1511 is used in the embodiment of the present invention, a product of Tixiai (Shanghai) Chemical Industry Development Co., Ltd.
- Isocyanate chain extender hexamethylene diisocyanate HDI is used in the examples of the present invention.
- JP-200 of Japan Soda Co., Ltd. is adopted;
- B-2000 of Japan Soda Co., Ltd. is used.
- thermoplastic starch master batch its steps comprise:
- thermoplastic starch masterbatch The starch after heat preservation is melted and extruded to make thermoplastic starch masterbatch.
- the starch is selected from corn starch, but other starches such as tapioca starch, rice starch, and potato starch can also be used.
- the unit of temperature in Table 2 is: °C, the unit of rotation speed is rpm, and the unit of time is minutes.
- thermoplastic starch masterbatches obtained in Examples 1-8 were respectively made into starch-based biodegradable films, and the steps were: blending 60 parts of thermoplastic starch masterbatches with 25 parts of PBSA and 20 parts of PBAT, and the film blowing temperature was 165° C. The blow-up ratio was 4:1, and the starch-based biodegradable film was prepared by blow molding.
- the PBSA used therein is the same as the PBSA added in the thermoplastic starch masterbatch.
- thermoplastic starch master batch its steps comprise:
- corn starch is used as starch.
- Example 17 100 parts of commercially available starch with a water content of 15%, Example 18 100 parts of commercially available starch with a water content of 22% Example 19 100 parts of commercially available starch with a water content of 30%
- Example 20 100 parts of commercially available starch with a water content of 22%, 1 part of oxidized starch
- Example 21 100 parts of commercially available starch with a water content of 22%, 3 parts of oxidized starch, 4 parts of hydroxypropyl starch
- Example 22 100 parts of commercially available starch with a water content of 22%, 10 parts of oxidized starch
- thermoplastic starch masterbatches obtained in Examples 17-22 were respectively made into starch-based biodegradable films, and the steps were: blending 60 parts of thermoplastic starch masterbatches with 25 parts of PBSA and 20 parts of PBAT, and the film blowing temperature was 165° C. The blow-up ratio was 4:1, and the starch-based biodegradable film was prepared by blow molding.
- the PBSA used therein is the same as the PBSA added in the thermoplastic starch masterbatch.
- modified starch can further improve the tensile strength and elongation of starch-based biodegradable films.
- thermoplastic starch master batch its steps comprise:
- thermoplastic starch masterbatch The starch after heat preservation is melted and extruded to make thermoplastic starch masterbatch.
- corn starch is used as starch.
- thermoplastic starch masterbatches obtained in Examples 29-34 were respectively made into starch-based biodegradable films, and the steps were: blending 60 parts of thermoplastic starch masterbatches with 25 parts of PBSA and 20 parts of PBAT, and the film blowing temperature was 165°C, The blow-up ratio was 4:1, and the starch-based biodegradable film was prepared by blow molding.
- the PBSA used therein is the same as the PBSA added in the thermoplastic starch masterbatch.
- thermoplastic starch masterbatches obtained in Comparative Example 1 were respectively made into starch-based biodegradable films, and the steps were as follows: blending 60 parts of thermoplastic starch masterbatches with 25 parts of PBSA and 20 parts of PBAT, the film blowing temperature was 165° C. The ratio was 4:1, and the starch-based biodegradable film of Comparative Example 2 was prepared by blow molding.
- the PBSA used therein is the same as the PBSA added in the thermoplastic starch masterbatch.
- adding a small amount of polybutadiene can further improve the tensile strength and elongation of starch-based biodegradable films.
- thermoplastic starch master batch of Example 1 respectively make starch-based biodegradable film, wherein the PBSA used is consistent with the PBSA component added in the thermoplastic starch master batch, and the proportioning and process parameters are shown in Table 8.
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Abstract
Description
淀粉 | |
实施例17 | 含水量15%的市售淀粉100份, |
实施例18 | 含水量22%的市售淀粉100份 |
实施例19 | 含水量30%的市售淀粉100份 |
实施例20 | 含水量22%的市售淀粉100份,氧化淀粉1份 |
实施例21 | 含水量22%的市售淀粉100份,氧化淀粉3份、羟丙基淀粉4份 |
实施例22 | 含水量22%的市售淀粉100份,氧化淀粉10份 |
Claims (17)
- 根据权利要求1所述的热塑性淀粉母粒,其特征在于:所述增塑剂为甘油、山梨醇、环氧大豆油中的一种或数种;聚丁二烯为端羟基聚丁二烯、环氧化聚丁二烯、1,2-聚丁二烯均聚物中的一种或数种;化学改性剂为马来酸酐、柠檬酸、甲基丙烯酸缩水甘油酯中的一种或数种;增粘剂为聚乙酸乙烯酯、乙烯-丙烯酸乙酯共聚物中的一种或两种、润滑剂为硬脂酸钙、油酸酰胺、芥酸酰胺中的一种或数种;填充剂为滑石粉、碳酸钙、硫酸钡、蒙脱土、云母粉的一种或数种;扩链剂为异氰酸酯类扩链剂、环氧类扩链剂、噁唑啉类扩链剂中的一种或数种的混合物。
- 根据权利要求2所述的热塑性淀粉母粒,其特征在于:所述聚丁二烯为端羟基聚丁二烯和环氧化聚丁二烯的混合物,其中端羟基聚丁二烯与环氧化聚丁二烯的比例为3:1-1:1wt。
- 根据权利要求2所述的热塑性淀粉母粒,其特征在于:还包括1-10份改性淀粉,所述改性淀粉为氧化淀粉、羟丙基淀粉中的一种或两种。
- 根据权利要求2所述的热塑性淀粉母粒,其特征在于:所述增粘剂为聚乙酸乙烯酯与乙烯-丙烯酸乙酯共聚物,聚乙酸乙烯酯与乙烯-丙烯酸乙酯共聚物的混合比例为3:1-1:1wt。
- 根据权利要求2所述的热塑性淀粉母粒,其特征在于:所述母粒用生物降解树脂为PBAT、PBSA中的一种或两种。
- 根据权利要求6所述的热塑性淀粉母粒,其特征在于:所述PBSA中,丁二酸占共聚比30-45%,己二酸占共聚比15-30%,丁二醇占共聚比40-55%。
- 根据权利要求1-7中任一项所述的热塑性淀粉母粒,其特征在于:第一次高速搅拌速度为600-1000转/分钟,时间为1-5分钟,第二次、第三次、第四次高速搅拌速度均为800-1200转/分钟,第二次高速搅拌的时间为5-20分钟,第三次高速搅拌的时间为5-15分钟,第四次高速搅拌的时间为1-5分钟,保温时间为2-12小时。
- 权利要求1-8中任一项所述的热塑性淀粉母粒的制备方法,其步骤包括:(1)取100份含水率在15-30%的淀粉,在室温下进行第一次高速搅拌;(2)升温至50-70℃,加入增塑剂、聚丁二烯和化学改性剂,进行第二次高速搅拌;(3)升温至75-95℃,加入增粘剂、润滑剂、填充剂、扩链剂,进行第三次高速搅拌;(4)加入母粒用生物降解树脂,进行第四次高速搅拌;(5)停止搅拌,保温处理;(6)保温后的淀粉混合物加入到双螺杆挤出机中,挤出、风冷、切粒,制成热塑性淀粉母粒。
- 根据权利要求9所述的热塑性淀粉母粒的制备方法,其特征在于:第一次高速搅拌速度为600-1000转/分钟,时间为1-5分钟,第二次、第三次、第四次高速搅拌速度均为800-1200转/分钟,第二次高速搅拌的时间为5-20分钟,第三次高速搅拌的时间为5-15分钟,第四次高速搅拌的时间为1-5分钟,保温时间为2-12小时。
- 根据权利要求10所述的热塑性淀粉母粒的制备方法,其特征在于:步骤(6)中采用双螺杆挤出机熔融挤出,双螺杆挤出机的长径比为44:1-60:1,温度范 围为110-160℃,螺杆转速为150-600rpm,挤出机末端具有抽真空排气功能模块。
- 根据权利要求10或11所述的热塑性淀粉母粒的制备方法,其特征在于:步骤(1)中还加入1-10份改性淀粉,所述改性淀粉为氧化淀粉、羟丙基淀粉中的一种或两种。
- 权利要求1-8所述的热塑性淀粉母粒在制备淀粉基生物降解薄膜中的应用。
- 一种淀粉基生物降解薄膜,其特征在于:由以下重量份的原料制备而成权利要求1-8所述的热塑性淀粉母粒 40-80份生物降解树脂 40-55份。
- 根据权利要求14所述的淀粉基生物降解薄膜,其特征在于:所述生物降解树脂为PLA、PBSA、PBAT、PPC中的一种或数种的混合物。
- 权利要求14或15所述的淀粉基生物降解薄膜的制备方法,其步骤为:将热塑性淀粉母粒与生物降解树脂进行共混,吹塑成型制得淀粉基生物降解薄膜。
- 根据权利要求16所述的淀粉基生物降解薄膜的制备方法,其特征在于:吹膜温度为145-175℃,吹胀比为3:1-5.5:1。
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