KR102630079B1 - Method for producing biodegradable polypropylene compound and biodegradable polypropylene compound prepared by using the same - Google Patents
Method for producing biodegradable polypropylene compound and biodegradable polypropylene compound prepared by using the same Download PDFInfo
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- KR102630079B1 KR102630079B1 KR1020210147092A KR20210147092A KR102630079B1 KR 102630079 B1 KR102630079 B1 KR 102630079B1 KR 1020210147092 A KR1020210147092 A KR 1020210147092A KR 20210147092 A KR20210147092 A KR 20210147092A KR 102630079 B1 KR102630079 B1 KR 102630079B1
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- Prior art keywords
- polypropylene
- thermoplastic starch
- polypropylene compound
- hydrophilic
- compound
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 126
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 126
- -1 polypropylene Polymers 0.000 title claims abstract description 112
- 150000001875 compounds Chemical class 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229920008262 Thermoplastic starch Polymers 0.000 claims abstract description 75
- 239000004628 starch-based polymer Substances 0.000 claims abstract description 75
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 238000013329 compounding Methods 0.000 claims abstract description 15
- 150000002978 peroxides Chemical class 0.000 claims abstract description 11
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 22
- 238000001125 extrusion Methods 0.000 claims description 15
- 229920000578 graft copolymer Polymers 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 229920000856 Amylose Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 33
- 229920002472 Starch Polymers 0.000 description 15
- 235000019698 starch Nutrition 0.000 description 14
- 239000008107 starch Substances 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 8
- 101150014929 TPS2 gene Proteins 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 6
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920002261 Corn starch Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- 229920006238 degradable plastic Polymers 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- 229920000945 Amylopectin Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000000654 additive Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000153158 Ammi visnaga Species 0.000 description 1
- 235000010585 Ammi visnaga Nutrition 0.000 description 1
- 229920001685 Amylomaize Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 1
- 101710194099 Thiamine-phosphate synthase 2 Proteins 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- WJSATVJYSKVUGV-UHFFFAOYSA-N hexane-1,3,5-triol Chemical compound CC(O)CC(O)CCO WJSATVJYSKVUGV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08K5/14—Peroxides
-
- 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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 a) 폴리프로필렌과 과산화물을 반응 압출하여 라디칼이 생성된 폴리프로필렌을 제조하는 단계; b) 상기 라디칼이 생성된 폴리프로필렌과 친수성 개질제를 반응 압출하여 폴리프로필렌 내 라디칼이 생성된 자리에 친수성 고분자를 결합시켜 친수성으로 개질된 폴리프로필렌 컴파운드를 제조하는 단계; 및 c) 상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분(Thermo Plastic Starch)을 컴파운딩하는 단계를 포함하는 생분해성 폴리프로필렌 컴파운드의 제조방법; 및 이에 따라 제조한 생분해성 폴리프로필렌 컴파운드에 관한 것이다.The present invention includes the steps of a) reacting and extruding polypropylene and peroxide to produce polypropylene in which radicals are generated; b) reacting and extruding the polypropylene in which the radicals were generated and a hydrophilic modifier to bind a hydrophilic polymer to the site where the radicals were generated in the polypropylene, thereby producing a hydrophilically modified polypropylene compound; and c) a method for producing a biodegradable polypropylene compound comprising the step of compounding the hydrophilic modified polypropylene compound with thermoplastic starch; and a biodegradable polypropylene compound prepared thereby.
Description
본 발명은 폴리프로필렌과 열가소성전분을 컴파운딩하는 단계를 포함하는 생분해성 폴리프로필렌 컴파운드의 제조방법 및 이에 따라 제조한 생분해성 폴리프로필렌 컴파운드에 관한 것이다.The present invention relates to a method for producing a biodegradable polypropylene compound comprising the step of compounding polypropylene and thermoplastic starch, and to a biodegradable polypropylene compound produced thereby.
전 세계적으로 플라스틱을 무분별하게 사용함으로써, 환경오염이 심각해지고 있다. 특히 플라스틱 폐기처리에 따른 환경문제 때문에 EU 에서는 탄소국경세 정책을 시행하고, 국제사회는 기후변화 문제의 심각성을 인식하고 이를 해결하기 위해 선진국에 의무를 부여하는 ‘교토의정서’채택에 이어 ‘파리협정’을 채택하여 탄소 중립(Net-Zero)를 실현하는 노력을 하고 있다. 이에 따라서 미국을 비롯한 구미 각국과 일본 등 세계 각국에서 여러가지 폐플라스틱 처리방안을 내놓고 있으며 플라스틱 자체로 썩어없어지는 분해성 플라스틱 개발에 비상한 관심을 기울이고 있다.Environmental pollution is becoming more serious due to the indiscriminate use of plastic around the world. In particular, due to environmental problems caused by plastic waste disposal, the EU implemented a carbon border tax policy, and the international community recognized the seriousness of the climate change problem and adopted the 'Kyoto Protocol', which imposes obligations on developed countries to solve it, followed by the 'Paris Agreement'. ', efforts are being made to realize carbon neutrality (Net-Zero). Accordingly, countries around the world, including the United States, Europe, America, and Japan, are coming up with various waste plastic disposal methods and are paying extraordinary attention to the development of degradable plastics that rot away on their own.
이러한 분해성 플라스틱은 광분해성 플라스틱(Photo Degradable Plastics)과 생분해성 플라스틱(Bio Degradable Plastics)으로 대별할 수 있다. 광분해성 플라스틱은 분해기간의 조절이 용이하며 빠른 분해속도를 가지는 반면, 땅속에서는 분해가 불가능하다는 단점을 가지고 있어서 사용상 많은 문제점을 안고 있으며, 생분해 플라스틱 제품은 대부분 물성이 약하거나, 단가가 높은 단점이 있다. 이러한 문제들로 인하여 현재 분해성 플라스틱의 시장 확대가 어려우며, 따라서 정부가 먼저 나서서 플라스틱 폐기물 규제를 진행하고, 생분해 또는 탄소절감 제품 사용을 강제하지 않는 이상 사용이 일반화되기 어려운 실정이다.These degradable plastics can be roughly divided into photo degradable plastics and biodegradable plastics. Photodegradable plastic is easy to control over the decomposition period and has a fast decomposition speed, but has the disadvantage of being impossible to decompose underground, which poses many problems in use. Most biodegradable plastic products have weak physical properties or high unit costs. there is. Due to these problems, it is currently difficult to expand the market for degradable plastics, and therefore, unless the government takes the initiative to regulate plastic waste and enforce the use of biodegradable or carbon-reducing products, it is difficult to generalize its use.
이러한 제반 문제를 해결하기 위하여, 전분을 이용한 생분해성 원료의 개발이 각광받고 있으며, 일부에서는 이를 쇼핑봉투, 이쑤시개 등에 활용하고 있다. 그러나, 종래의 전분 등을 이용하여 제조된 생분해성 플라스틱 제품의 경우, 강도 및 내충격성이 실용기준에 못 미치거나, 실제로는 생분해능이 떨어져서, 미생물에 의해 분해되기 위해서는 많은 시간이 소요되는 등의 문제점이 있다.In order to solve these problems, the development of biodegradable raw materials using starch is receiving attention, and some are using it for shopping bags, toothpicks, etc. However, in the case of biodegradable plastic products manufactured using conventional starch, etc., there are problems such as strength and impact resistance falling below practical standards, or biodegradability is actually low, so it takes a lot of time to be decomposed by microorganisms. There is.
본 발명은 생활/산업용으로 폭넓게 이용되고 있는 비분해성 폴리프로필렌 제품을 대체하는 친환경적인 생분해성 폴리프로필렌 소재를 제공하기 위한 것이다.The present invention is intended to provide an eco-friendly, biodegradable polypropylene material that replaces non-degradable polypropylene products that are widely used for household/industrial purposes.
본 발명은 생분해성 폴리프로필렌 컴파운드의 제조방법을 제공하기 위한 것이다.The present invention is intended to provide a method for producing a biodegradable polypropylene compound.
본 발명은 상기 제조방법에 따라 제조한 생분해성 폴리프로필렌 컴파운드를 제공하기 위한 것이다.The present invention is to provide a biodegradable polypropylene compound manufactured according to the above manufacturing method.
본 발명의 일 실시예는 a) 폴리프로필렌과 과산화물을 반응 압출하여 라디칼이 생성된 폴리프로필렌을 제조하는 단계; b) 상기 라디칼이 생성된 폴리프로필렌과 친수성 개질제를 반응 압출하여 폴리프로필렌 내 라디칼이 생성된 자리에 친수성 고분자를 결합시켜 친수성으로 개질된 폴리프로필렌 컴파운드를 제조하는 단계; 및 c) 상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분(Thermo Plastic Starch)을 컴파운딩하는 단계를 포함하는 생분해성 폴리프로필렌 컴파운드의 제조방법을 제공한다.One embodiment of the present invention includes the steps of a) reacting and extruding polypropylene and peroxide to produce polypropylene in which radicals are generated; b) reacting and extruding the polypropylene in which the radicals were generated and a hydrophilic modifier to bind a hydrophilic polymer to the site where the radicals were generated in the polypropylene, thereby producing a hydrophilically modified polypropylene compound; and c) providing a method for producing a biodegradable polypropylene compound comprising the step of compounding the hydrophilic modified polypropylene compound with thermoplastic starch.
또한, 본 발명의 다른 실시예는 친수성으로 개질된 폴리프로필렌 컴파운드; 및 열가소성전분(Thermo Plastic Starch)을 컴파운딩하여 제조한 생분해성 폴리프로필렌 컴파운드를 제공한다.In addition, another embodiment of the present invention is a hydrophilic modified polypropylene compound; and a biodegradable polypropylene compound manufactured by compounding thermoplastic starch.
본 발명에 따라 친수성으로 개질된 폴리프로필렌과 비결정성영역 아밀로오스 함량이 높은 나노입자 형태의 열가소성전분(TPS)를 컴파운딩함으로써 인장강도가 기존의 폴리프로필렌 수준 이상이면서도 생분해능이 뛰어난 생분해성 폴리프로필렌 컴파운드를 제조할 수 있다.According to the present invention, by compounding hydrophilic modified polypropylene and thermoplastic starch (TPS) in the form of nanoparticles with a high amylose content in the amorphous region, a biodegradable polypropylene compound with a tensile strength higher than that of conventional polypropylene and excellent biodegradability is produced. It can be manufactured.
이하에서, 본 발명을 상세하게 설명한다.Below, the present invention is described in detail.
본 발명의 기술적 사상 및 범위를 벗어나지 않는 범위 내에서 본 발명의 다양한 변경 및 변형이 가능하다는 점은 당업자에게 자명할 것이다. 따라서, 본 발명은 특허청구범위에 기재된 발명 및 그 균등물의 범위 내에 드는 변경 및 변형을 모두 포함한다.It will be apparent to those skilled in the art that various changes and modifications may be made to the present invention without departing from the technical spirit and scope of the present invention. Accordingly, the present invention includes all changes and modifications that fall within the scope of the invention recited in the claims and equivalents thereof.
본 명세서에서 언급된 '포함한다', '갖는다', '이루어진다' 등이 사용되는 경우 '~만'이라는 표현이 사용되지 않는 이상 다른 부분이 추가될 수 있다. 구성 요소가 단수로 표현된 경우, 특별히 명시적인 기재 사항이 없는 한 복수를 포함한다. 또한, 구성 요소를 해석함에 있어서, 별도의 명시적 기재가 없더라도 오차 범위를 포함하는 것으로 해석된다.When 'includes', 'has', 'consists of', etc. mentioned in this specification are used, other parts may be added unless the expression 'only' is used. If a component is expressed in the singular, the plural is included unless specifically stated. In addition, when interpreting a component, it is interpreted to include a margin of error even if there is no separate explicit description.
본 발명의 일 실시예에 따른 생분해성 폴리프로필렌 컴파운드의 제조방법은 The method for producing a biodegradable polypropylene compound according to an embodiment of the present invention is
a) 폴리프로필렌과 과산화물을 반응 압출하여 라디칼이 생성된 폴리프로필렌을 제조하는 단계;a) reacting and extruding polypropylene and peroxide to produce radical-generated polypropylene;
b) 상기 라디칼이 생성된 폴리프로필렌과 친수성 개질제를 반응 압출하여 폴리프로필렌 내 라디칼이 생성된 자리에 친수성 고분자를 결합시켜 친수성으로 개질된 폴리프로필렌 컴파운드를 제조하는 단계; 및b) reacting and extruding the polypropylene in which the radicals were generated and a hydrophilic modifier to bind a hydrophilic polymer to the site where the radicals were generated in the polypropylene, thereby producing a hydrophilically modified polypropylene compound; and
c) 상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분(Thermo Plastic Starch)을 컴파운딩하는 단계를 포함한다. c) Comprising the step of compounding the hydrophilic modified polypropylene compound and thermoplastic starch.
상기 단계 a)에서, 폴리프로필렌과 과산화물은 반응 압출되어 폴리프로필렌 내에 라디칼이 생성될 수 있다.In step a), polypropylene and peroxide may be reacted and extruded to generate radicals in polypropylene.
상기 단계 a)에서, 폴리프로필렌(PP)은 프로필렌의 중합에 의하여 만들어질 수 있다. 본 발명의 일 실시예에 있어서, 폴리프로필렌(PP)의 종류에 특별한 제한이 있는 것은 아니다.In step a), polypropylene (PP) can be made by polymerization of propylene. In one embodiment of the present invention, there is no particular limitation on the type of polypropylene (PP).
상기 단계 a)에서, 상기 과산화물은 분자 내에 과산화 이온(O2 2-)을 포함하는 산화물로 폴리프로필렌과 반응 압출되어 폴리프로필렌에 라디칼을 생성할 수 있다.In step a), the peroxide is an oxide containing peroxide ions (O 2 2- ) in the molecule, and can be reacted and extruded with polypropylene to generate radicals in polypropylene.
상기 과산화물은 M½O2 (M1=H, Li, Na, K, NH4, Rb, Cs), M1O2(M1=Mg, Ca, Sr, Ba, Zn, Cd, Hg) 등의 무기 과산화물; R-O-O-R(R=H, CnH2n), 또는 과산화아실 RCO-O-O-OCR(R=H, CnH2n) 등의 유기 과산화물일 수 있다. 일 례로 퍼옥사이드, 과산화수소(H2O2) 등을 사용할 수 있다.The peroxide is inorganic such as M½O 2 (M 1 =H, Li, Na, K, NH 4 , Rb, Cs), M 1 O 2 (M 1 =Mg, Ca, Sr, Ba, Zn, Cd, Hg) peroxide; It may be an organic peroxide such as ROOR (R=H, C n H 2n ), or acyl peroxide RCO-OO-OCR (R=H, C n H 2n ). For example, peroxide, hydrogen peroxide (H 2 O 2 ), etc. can be used.
상기 단계 b)에서, 상기 친수성 개질제는 상기 라디칼이 생성된 폴리프로필렌과 반응 압출되어 폴리프로필렌 내 라디칼이 생성된 자리에 친수성 고분자를 결합시켜 친수성으로 개질된 폴리프로필렌 컴파운드를 제조한다.In step b), the hydrophilic modifier is reacted and extruded with the polypropylene in which the radical was generated to bind a hydrophilic polymer to the site where the radical was generated in the polypropylene, thereby producing a hydrophilically modified polypropylene compound.
상기 친수성 개질제는 극성을 부여하는 친수성 고분자를 포함하는 에틸렌 비닐아세테이트(EVA), 에틸렌 메틸 아크릴레이트(EMA), MAH graftmer(Maleic Anhydride Grafted Polymer) 등일 수 있다.The hydrophilic modifier may be ethylene vinyl acetate (EVA), ethylene methyl acrylate (EMA), MAH graftmer (Maleic Anhydride Grafted Polymer), etc., which contain a hydrophilic polymer that imparts polarity.
바람직하게는 친수성 개질제는 MAH graftmer(Maleic Anhydride Grafted Polymer)일 수 있다. 본 발명자들은 친수성 개질제로 MAH graftmer(Maleic Anhydride Grafted Polymer)를 사용하였을 때 인장강도가 가장 높게 상승한 것을 확인하였다.Preferably, the hydrophilic modifier may be MAH graftmer (Maleic Anhydride Grafted Polymer). The present inventors confirmed that the tensile strength increased the highest when MAH graftmer (Maleic Anhydride Grafted Polymer) was used as a hydrophilic modifier.
상기 친수성 개질제는 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분의 총 중량에 대하여 1 내지 3 중량%로 사용되는 것이 바람직하다.The hydrophilic modifier is preferably used in an amount of 1 to 3% by weight based on the total weight of the hydrophilically modified polypropylene compound and thermoplastic starch.
상기 단계 c)에서, 상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분(Thermo Plastic Starch)은 컴파운딩되어 생분해성 폴리프로필렌 컴파운드가 제조된다.In step c), the hydrophilic modified polypropylene compound and thermoplastic starch are compounded to produce a biodegradable polypropylene compound.
상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분의 혼합중량비는 50 : 50 내지 90 : 10 인 것일 수 있다. The mixing weight ratio of the hydrophilic modified polypropylene compound and thermoplastic starch may be 50:50 to 90:10.
상기 열가소성전분(Thermo Plastic Starch)은 하나 이상의 가소제를 포함하는 전분의 파괴된 형태일 수 있다.The thermoplastic starch may be a destroyed form of starch containing one or more plasticizers.
전분은 두 형태의 알파-D-글루코오스 폴리머: 아밀로오스, 약 1 x 105의 분자량을 가진 실질적으로 선형인 폴리머; 아밀로펙틴, 약 1 x 107의 분자량을 가진 가지가 많은 폴리머로 구성된다. 각각의 반복하는 글루코오스 단위는 통상적으로 3개의 유리 하이드록실기를 가져서, 폴리머에 친수성과 반응성 작용기들을 제공한다. 대부분의 전분은 20 내지 30% 아밀로오스 및 70 내지 80% 아밀로펙틴을 포함한다. Starch is an alpha-D-glucose polymer of two forms: amylose, a substantially linear polymer with a molecular weight of about 1 x 10 5 ; Amylopectin, a highly branched polymer with a molecular weight of approximately 1 x 10 7 . Each repeating glucose unit typically has three free hydroxyl groups, providing hydrophilic and reactive functional groups to the polymer. Most starches contain 20 to 30% amylose and 70 to 80% amylopectin.
상기 열가소성전분은 비결정성영역의 아밀로오스 함량이 50 내지 90%, 바람직하게는 70 내지 90% 일 수 있다.The thermoplastic starch may have an amylose content in the amorphous region of 50 to 90%, preferably 70 to 90%.
본 발명의 일 실시예에서, 비결정성영역의 아밀로오스 함량이 50% 이상인 경우 얻어지는 폴리프로필렌 수지 컴파운드의 ASTM D6954에 의한 생분해도가 55% 이상으로 증가함을 확인하였다.In one example of the present invention, it was confirmed that when the amylose content in the amorphous region was 50% or more, the biodegradability of the obtained polypropylene resin compound according to ASTM D6954 increased to 55% or more.
상기 열가소성전분(Thermo Plastic Starch)은 나노사이즈의 입자크기를 갖는 나노입자일 수 있다. 열가소성전분은 나노입자 형태로 폴리프로필렌과 컴파운딩됨으로써 폴리프로필렌 전체에 골고루 분산될 수 있고 그 결과 생분해성을 증가시킬 수 있다. 바람직하게는, 상기 열가소성전분은 10 내지 300 nm, 바람직하게는 50 내지 200 nm의 입자크기를 갖는 것일 수 있다. 본 발명의 일 실시예에서, 열가소성전분의 입자크기가 100 nm인 경우 얻어지는 폴리프로필렌 수지 컴파운드의 ASTM D6954에 의한 생분해도가 55% 이상으로 증가함을 확인하였다.The thermoplastic starch may be nanoparticles having a nano-sized particle size. By compounding polypropylene in the form of nanoparticles, thermoplastic starch can be evenly dispersed throughout the polypropylene and, as a result, can increase biodegradability. Preferably, the thermoplastic starch may have a particle size of 10 to 300 nm, preferably 50 to 200 nm. In one example of the present invention, it was confirmed that when the particle size of thermoplastic starch was 100 nm, the biodegradability of the obtained polypropylene resin compound according to ASTM D6954 increased to more than 55%.
상기 열가소성전분(Thermo Plastic Starch)은 하나 이상의 다가 알콜 가소제를 포함하는 것일 수 있다. The thermoplastic starch may contain one or more polyhydric alcohol plasticizers.
전분은 일반적으로 나쁜 열가소성 특성을 나타낸다. 이런 특성을 향상시키기 위해서, 전분은 당업계에 주지된 수단에 의해 열가소성전분(Thermo Plastic Starch)으로 변환될 수 있다. 예를 들어, 천연 전분 또는 화학적으로 변형된 전분은 하나 이상의 가소제와 용융 처리될 수 있다.Starch generally exhibits poor thermoplastic properties. To improve these properties, starch can be converted to thermoplastic starch by means well known in the art. For example, natural starch or chemically modified starch can be melt treated with one or more plasticizers.
적절한 다가 알콜은 글리세롤, 에틸렌 글리콜, 프로필렌 글리콜, 에틸렌 다이글리콜, 프로필렌 다이글리콜, 에틸렌 트라이글리콜, 프로필렌 트라이글리콜, 폴리에틸렌 글리콜, 폴리프로필렌 글리콜, 1,2-프로페인다이올, 1,3-프로페인다이올, 1,2-부테인다이올, 1,3-부테인다이올, 1,4-부테인다이올, 1,5-펜테인다이올, 1,6-헥세인다이올, 1,5-헥세인다이올, 1,2,6-헥세인트라이올, 1,3,5-헥세인트라이올, 네오-펜틸 글리콜, 트라이메틸올 프로페인, 펜타에리트리톨, 만니톨, 소르비톨 및 이의 아세테이트, 에톡실레이트 및 프로폭실레이트 유도체를 포함하나 이에 제한되지 않는다. 일 실시예에서, 상기 열가소성전분(Thermo Plastic Starch)은 글리세롤 및/또는 소르비톨 가소제를 포함한다.Suitable polyhydric alcohols include glycerol, ethylene glycol, propylene glycol, ethylene diglycol, propylene diglycol, ethylene triglycol, propylene triglycol, polyethylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propane. Diol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 5-hexanediol, 1,2,6-hexanetriol, 1,3,5-hexanetriol, neo-pentyl glycol, trimethylol propane, pentaerythritol, mannitol, sorbitol and its acetate , ethoxylate and propoxylate derivatives. In one embodiment, the thermoplastic starch includes glycerol and/or sorbitol plasticizer.
열가소성전분(Thermo Plastic Starch)의 가소제 함량은 일반적으로 전분 및 가소제 성분을 합한 질량에 대해 약 5중량% 내지 약 50중량%, 예를 들어, 약 10중량% 내지 약 40중량% 또는 약 10중량% 내지 약 30중량%일 수 있다.The plasticizer content of thermoplastic starch is generally about 5% by weight to about 50% by weight, for example, about 10% by weight to about 40% by weight, or about 10% by weight, based on the combined mass of starch and plasticizer components. It may be from about 30% by weight.
본 발명에서 열가소성전분(Thermo Plastic Starch)의 중량%에 대한 언급은 열가소성전분(Thermo Plastic Starch)의 전분 및 가소제 구성 성분의 전체 질량을 포함하는 것을 의미한다.In the present invention, reference to the weight percent of thermoplastic starch (Thermo Plastic Starch) means including the total mass of the starch and plasticizer components of thermoplastic starch (Thermo Plastic Starch).
열가소성전분(Thermo Plastic Starch)이 유도될 수 있는 전분은 옥수수 전분, 감자 전분, 밀 전분, 대두 전분, 타피오카 전분, 고 아밀로오스 전분 또는 이의 조합을 포함하나 이에 제한되지 않는다.Starches from which thermoplastic starch can be derived include, but are not limited to, corn starch, potato starch, wheat starch, soybean starch, tapioca starch, high amylose starch, or combinations thereof.
본 발명의 일 실시예에서, 열가소성전분(Thermo Plastic Starch)을 제조하는데 사용된 전분은 DS > 0.1을 가진 옥수수 전분 또는 옥수수 전분 아세트산염이다.In one embodiment of the invention, the starch used to prepare Thermo Plastic Starch is corn starch or corn starch acetate with DS > 0.1.
본 발명에서 "컴파운딩"은 고분자원재료에 여러 종류의 첨가제나 보강재 등을 가하여 사용목적에 적합하고 압출, 사출 등의 성형가공이 가능한 중간제품을 제조하는 공정을 의미한다. 본 발명에서 "컴파운딩"은 "반응 압출(reactive extrusion)" 단계를 포함할 수 있다. "반응 압출(reactive extrusion)"은 고분자 및 중합될 수 있는 단량체가 압출 성형되는 과정에서 화학반응이 의도적으로 일어나도록 하는 연속 가공형태를 의미한다.In the present invention, “compounding” refers to the process of adding various types of additives or reinforcing materials to polymer raw materials to produce intermediate products that are suitable for the intended use and can be subjected to molding processing such as extrusion or injection. In the present invention, “compounding” may include a “reactive extrusion” step. “Reactive extrusion” refers to a form of continuous processing in which chemical reactions are intentionally caused to occur during the extrusion process of polymers and polymerizable monomers.
본 발명에서 컴파운딩 또는 반응압출은 190 내지 210℃에서 가열한 후 압출하는 단계를 포함할 수 있다. 가열 온도가 190℃ 미만이면 폴리프로필렌이 융해되지 않을 수 있고, 210℃ 초과이면 열가소성전분이 탄화되어 증기(fume)이 발생할 수 있다.In the present invention, compounding or reaction extrusion may include heating at 190 to 210°C and then extruding. If the heating temperature is less than 190℃, polypropylene may not melt, and if it exceeds 210℃, the thermoplastic starch may carbonize and generate fume.
상기 압출단계는 압출기를 사용하여 150 내지 250 rpm의 스크류 속도로 압출하는 단계일 수 있다.The extrusion step may be a step of extruding at a screw speed of 150 to 250 rpm using an extruder.
스크류 속도가 150 rpm 미만일 경우 생분해성 폴리프로필렌 컴파운드의 인장강도 및 생분해도가 미흡할 수 있고, 스크류 속도가 250 rpm를 벗어날 경우 연기와 변색이 발생하면서 용융수지에 열화(degradation)를 일으킬 수 있다.If the screw speed is less than 150 rpm, the tensile strength and biodegradability of the biodegradable polypropylene compound may be insufficient, and if the screw speed exceeds 250 rpm, smoke and discoloration may occur, which may cause degradation of the molten resin.
상기 압출기는 트윈스크류압출설비(TSE)를 포함할 수 있다. 트윈스크류압출설비(TSE)는 폴리머를 첨가제 및 충전재와 연속적으로 혼합하기 위해 컴파운딩 업계에서 가장 널리 사용되는 장치다.The extruder may include a twin screw extrusion equipment (TSE). Twin-screw extrusion equipment (TSE) is the most widely used device in the compounding industry for continuously mixing polymers with additives and fillers.
상기 압출기는 배럴, 믹싱존 및 압출다이의 온도가 모두 다르게 포함할 수 있다. The extruder may have different temperatures for the barrel, mixing zone, and extrusion die.
본 발명의 다른 실시예에 따른 생분해성 폴리프로필렌 컴파운드는 친수성으로 개질된 폴리프로필렌 컴파운드; 및 열가소성전분을 컴파운딩하여 제조될 수 있다.A biodegradable polypropylene compound according to another embodiment of the present invention includes a hydrophilic modified polypropylene compound; And it can be manufactured by compounding thermoplastic starch.
상기 생분해성 폴리프로필렌 수지 컴파운드는 상기 생분해성 폴리프로필렌 컴파운드의 제조방법에 따라 제조될 수 있다.The biodegradable polypropylene resin compound can be manufactured according to the method for producing the biodegradable polypropylene compound.
상기 친수성으로 개질된 폴리프로필렌 컴파운드는 폴리프로필렌, 과산화물 및 친수성 개질제를 반응 압출하여 제조한 것일 수 있다.The hydrophilic modified polypropylene compound may be manufactured by reaction extrusion of polypropylene, peroxide, and a hydrophilic modifier.
상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분의 혼합중량비는 50 : 50 내지 90 : 10 인 것일 수 있다.The mixing weight ratio of the hydrophilic modified polypropylene compound and thermoplastic starch may be 50:50 to 90:10.
상기 열가소성전분은 비결정성영역의 아밀로오스 함량이 50 내지 90%, 바람직하게는 70 내지 90% 일 수 있다.The thermoplastic starch may have an amylose content in the amorphous region of 50 to 90%, preferably 70 to 90%.
본 발명의 일 실시예에 따르면, 상기 생분해성 폴리프로필렌 컴파운드는 ASTM D638 기준으로 인장강도가 350 kgf/㎤ 이상, 바람직하게는 380 kgf/㎤ 이상일 수 있다.According to one embodiment of the present invention, the biodegradable polypropylene compound may have a tensile strength of 350 kgf/cm3 or more, preferably 380 kgf/cm3 or more, based on ASTM D638.
본 발명의 일 실시예에 따르면, 상기 생분해성 폴리프로필렌 컴파운드는 ASTM D638 기준으로 생분해도가 40 % 이상, 바람직하게는 50% 이상일 수 있다.According to one embodiment of the present invention, the biodegradable polypropylene compound may have a biodegradability of 40% or more, preferably 50% or more, based on ASTM D638.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 하기 실시예에 의해 본 발명의 내용이 한정되는 것은 아니다.Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are provided only to make the present invention easier to understand, and the content of the present invention is not limited by the following examples.
<실시예 1><Example 1>
폴리프로필렌 75 중량%에 벤조일퍼옥사이드 1000 내지 2000 ppm을 첨가한 후 210 ℃, 200 rpm의 조건으로 반응 압출한 후 MAH graftmer(Maleic Anhydride Grafted Polymer)를 첨가한 후 210 ℃, 200 rpm의 조건으로 반응 압출하여 친수성으로 개질된 폴리프로필렌 컴파운드를 제조하였다. 상기 친수성으로 개질된 폴리프로필렌 컴파운드에 열가소성전분(옥수수 전분 95 중량% 및 글리세롤 가소제 5 중량%) 25 중량%를 첨가한 후 210 ℃, 200 rpm의 조건으로 반응 압출하여 폴리프로필렌 컴파운드를 제조하였다.After adding 1000 to 2000 ppm of benzoyl peroxide to 75% by weight of polypropylene, reaction and extrusion were performed at 210°C and 200 rpm, and then MAH graftmer (Maleic Anhydride Grafted Polymer) was added and reaction was performed at 210°C and 200 rpm. A hydrophilic modified polypropylene compound was manufactured by extrusion. A polypropylene compound was prepared by adding 25% by weight of thermoplastic starch (95% by weight of corn starch and 5% by weight of glycerol plasticizer) to the hydrophilic modified polypropylene compound and then extruding the reaction at 210°C and 200 rpm.
이 때 MAH graftmer(Maleic Anhydride Grafted Polymer)는 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분의 총 중량에 대하여 2 중량%로 사용하였다.At this time, MAH graftmer (Maleic Anhydride Grafted Polymer) was used at 2% by weight based on the total weight of the hydrophilically modified polypropylene compound and thermoplastic starch.
또한, 열가소성전분은 입자크기가 100 nm이고, 비결정성영역의 함량이 50%이었다. In addition, the thermoplastic starch had a particle size of 100 nm and an amorphous region content of 50%.
<실시예 2><Example 2>
열가소성전분의 비결정성영역의 함량이 70%인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as Example 1, except that the content of the amorphous region of thermoplastic starch was 70%.
<비교예 1> <Comparative Example 1>
대조군으로 폴리프로필렌을 사용하였다.Polypropylene was used as a control.
<비교예 2><Comparative Example 2>
개질하지 않은 폴리프로필렌을 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that unmodified polypropylene was used, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%.
<비교예 3> <Comparative Example 3>
친수성 개질제로서 EVA 1 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 1% by weight of EVA was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%.
<비교예 4> <Comparative Example 4>
친수성 개질제로서 EVA 2 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 2% by weight of EVA was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%.
<비교예 5> <Comparative Example 5>
친수성 개질제로서 EVA 3 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 3% by weight of EVA was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%.
<비교예 6> <Comparative Example 6>
친수성 개질제로서 EMA 1 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 1% by weight of EMA was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%.
<비교예 7> <Comparative Example 7>
친수성 개질제로서 EMA 2 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 2% by weight of EMA was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%.
<비교예 8> <Comparative Example 8>
친수성 개질제로서 EMA 3 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 3% by weight of EMA was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%.
<비교예 9> <Comparative Example 9>
친수성 개질제로서 MAH graftmer(Maleic Anhydride Grafted Polymer) 1 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 1% by weight of MAH graftmer (Maleic Anhydride Grafted Polymer) was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%. Manufactured.
<비교예 10> <Comparative Example 10>
열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that the particle size of the thermoplastic starch was 5㎛ and the content of the amorphous region was 30%.
<비교예 11> <Comparative Example 11>
친수성 개질제로서 MAH graftmer(Maleic Anhydride Grafted Polymer) 3 중량%를 사용하고 열가소성전분의 입자크기가 5㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that 3% by weight of MAH graftmer (Maleic Anhydride Grafted Polymer) was used as a hydrophilic modifier, the particle size of the thermoplastic starch was 5㎛, and the content of the amorphous region was 30%. Manufactured.
<비교예 12> <Comparative Example 12>
열가소성전분의 입자크기가 3㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that the particle size of the thermoplastic starch was 3㎛ and the content of the amorphous region was 30%.
<비교예 13> <Comparative Example 13>
열가소성전분의 입자크기가 1㎛ 이고 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as in Example 1, except that the particle size of the thermoplastic starch was 1㎛ and the content of the amorphous region was 30%.
<비교예 14> <Comparative Example 14>
열가소성전분의 비결정성영역의 함량이 30% 인 것을 제외하고는 실시예 1과 동일한 방법으로 폴리프로필렌 컴파운드를 제조하였다.A polypropylene compound was prepared in the same manner as Example 1, except that the content of the amorphous region of thermoplastic starch was 30%.
<실험예><Experimental example>
상기 실시예 1 내지 2에서 제조한 폴리프로필렌 컴파운드와 비교예 1 내지 14에서 제조한 폴리프로필렌 컴파운드의 인장강도 및 생분해도를 측정하여 그 결과를 하기 표 1에 나타내었다. 이 때 인장강도는 ASTM D638에 따라 측정하였고, 생분해도는 ASTM D6954에 따라 측정하였다.The tensile strength and biodegradability of the polypropylene compounds prepared in Examples 1 to 2 and the polypropylene compounds prepared in Comparative Examples 1 to 14 were measured, and the results are shown in Table 1 below. At this time, tensile strength was measured according to ASTM D638, and biodegradability was measured according to ASTM D6954.
[kgf/㎠]tensile strength
[kgf/㎠]
상기 표 1의 비교예 1과 2를 대비하면, 기존의 폴리프로필렌(PP)에 열가소성전분(TPS)을 첨가하면 인장강도가 360 kgf/㎠에서 192 kgf/㎠로 낮아짐을 알 수 있었다.Comparing Comparative Examples 1 and 2 in Table 1 above, it was found that adding thermoplastic starch (TPS) to existing polypropylene (PP) lowered the tensile strength from 360 kgf/cm2 to 192 kgf/cm2.
또한, 상기 표 1의 비교예 3 내지 비교예 8를 참조하면, 친수성 개질제로 MAH graftmer를 사용할 경우 인장강도가 가장 높게 상승함을 알 수 있었다. 나아가, MAH graftmer의 최적의 함량은 2중량% 이상임을 알 수 있었다.In addition, referring to Comparative Examples 3 to 8 in Table 1, it was found that the tensile strength increased the highest when MAH graftmer was used as the hydrophilic modifier. Furthermore, it was found that the optimal content of MAH graftmer was more than 2% by weight.
또한, MAH graftmer의 함량이 2중량%인 상기 표 1의 비교예 10, 비교예 13과 비교예 14를 대비하면, 열가소성전분(TPS)의 입자크기를 줄이면 줄일수록 생분해도가 높아지는 것을 알 수 있었다.In addition, when comparing Comparative Examples 10, 13, and 14 of Table 1, where the content of MAH graftmer is 2% by weight, it was found that the more the particle size of thermoplastic starch (TPS) is reduced, the higher the biodegradability. .
또한, MAH graftmer의 함량이 2중량%이고, 열가소성전분(TPS)의 입자크기가 100 nm인 비교예 14와, 실시예 1 내지 2를 대비하면, 열가소성전분(TPS)의 비결정성영역의 함량이 클수록 생분해도가 높아지는 것을 알 수 있었다.In addition, when comparing Comparative Example 14, in which the content of MAH graftmer is 2% by weight and the particle size of thermoplastic starch (TPS) is 100 nm, and Examples 1 to 2, the content of the amorphous region of thermoplastic starch (TPS) is It was found that the larger the size, the higher the biodegradability.
결론적으로 폴리프로필렌 75 중량%, 친수성 개질제로서 MAH graftmer 2 중량%, 입자크기가 100 nm이고 비결정성영역의 함량이 70%인 열가소성전분(TPS) 25 중량%로 제조한 실시예 2의 폴리프로필렌 컴파운드가 인장강도가 382 kgf/㎠로 가장 높고 생분해도도 65%로 가장 높은 것을 확인하였다. In conclusion, the polypropylene compound of Example 2 was prepared with 75% by weight of polypropylene, 2% by weight of MAH graftmer as a hydrophilic modifier, and 25% by weight of thermoplastic starch (TPS) with a particle size of 100 nm and an amorphous region content of 70%. It was confirmed that the tensile strength was the highest at 382 kgf/cm2 and the biodegradability was also the highest at 65%.
Claims (13)
b) 상기 라디칼이 생성된 폴리프로필렌과 친수성 개질제를 반응 압출하여 폴리프로필렌 내 라디칼이 생성된 자리에 친수성 고분자를 결합시켜 친수성으로 개질된 폴리프로필렌 컴파운드를 제조하는 단계; 및
c) 상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분(Thermo Plastic Starch)을 컴파운딩하는 단계를 포함하고,
상기 친수성 개질제는 극성을 부여하는 친수성 고분자를 포함하는 MAH graftmer(Maleic Anhydride Grafted Polymer)이고,
상기 열가소성전분은 10 내지 300 nm의 입자크기를 갖고,
상기 열가소성전분은 비결정성영역의 아밀로오스 함량이 50 내지 90%인 것인,
ASTM D638 기준으로 인장강도가 380 kgf/㎤ 이상이고, ASTM D6954 기준으로생분해도가 50 % 이상인 생분해성 폴리프로필렌 컴파운드의 제조방법.
a) reacting and extruding polypropylene and peroxide to produce radical-generated polypropylene;
b) reacting and extruding the polypropylene in which the radicals were generated and a hydrophilic modifier to bind a hydrophilic polymer to the site where the radicals were generated in the polypropylene, thereby producing a hydrophilically modified polypropylene compound; and
c) Comprising the step of compounding the hydrophilic modified polypropylene compound and thermoplastic starch,
The hydrophilic modifier is MAH graftmer (Maleic Anhydride Grafted Polymer) containing a hydrophilic polymer that imparts polarity,
The thermoplastic starch has a particle size of 10 to 300 nm,
The thermoplastic starch has an amylose content of 50 to 90% in the amorphous region,
A method of manufacturing a biodegradable polypropylene compound with a tensile strength of 380 kgf/cm3 or more based on ASTM D638 and a biodegradability of 50% or more based on ASTM D6954.
상기 친수성 개질제는 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분의 총 중량에 대하여 1 내지 3 중량%로 사용되는 것인, 제조방법.
According to paragraph 1,
The hydrophilic modifier is used in an amount of 1 to 3% by weight based on the total weight of the hydrophilically modified polypropylene compound and thermoplastic starch.
상기 단계 c)에서, 상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분의 혼합중량비는 50 : 50 내지 90 : 10 인 것인, 제조방법.
According to paragraph 1,
In step c), the mixing weight ratio of the hydrophilic modified polypropylene compound and thermoplastic starch is 50:50 to 90:10.
상기 컴파운딩 또는 반응 압출은 190 내지 210℃에서 가열한 후 압출하는 단계를 포함하는 것인, 제조방법.
According to paragraph 1,
The compounding or reaction extrusion is a manufacturing method comprising heating at 190 to 210°C and then extruding.
상기 압출단계는 압출기를 사용하여 150 내지 250 rpm의 스크류 속도로 압출하는 단계인 것인, 제조방법.
In clause 7,
The extrusion step is a manufacturing method that involves extruding at a screw speed of 150 to 250 rpm using an extruder.
상기 친수성으로 개질된 폴리프로필렌 컴파운드는 폴리프로필렌, 과산화물 및 친수성 개질제를 반응 압출하여 제조한 것이고,
상기 친수성 개질제는 극성을 부여하는 친수성 고분자를 포함하는 MAH graftmer(Maleic Anhydride Grafted Polymer)이고,
상기 열가소성전분은 10 내지 300 nm의 입자크기를 갖고,
상기 열가소성전분은 비결정성영역의 아밀로오스 함량이 50 내지 90%인 것인,
ASTM D638 기준으로 인장강도가 380 kgf/㎤ 이상이고,
ASTM D6954 기준으로생분해도가 50 % 이상인 것인,
생분해성 폴리프로필렌 컴파운드.
Hydrophilically modified polypropylene compound; and a biodegradable polypropylene compound manufactured by compounding thermoplastic starch,
The hydrophilic modified polypropylene compound is manufactured by reaction extrusion of polypropylene, peroxide, and hydrophilic modifier,
The hydrophilic modifier is MAH graftmer (Maleic Anhydride Grafted Polymer) containing a hydrophilic polymer that imparts polarity,
The thermoplastic starch has a particle size of 10 to 300 nm,
The thermoplastic starch has an amylose content of 50 to 90% in the amorphous region,
Based on ASTM D638, the tensile strength is more than 380 kgf/㎤,
Based on ASTM D6954, biodegradability is 50% or more,
Biodegradable polypropylene compound.
상기 친수성으로 개질된 폴리프로필렌 컴파운드와 열가소성전분의 혼합중량비는 50 : 50 내지 90 : 10 인 것인, 생분해성 폴리프로필렌 컴파운드.
According to clause 9,
A biodegradable polypropylene compound, wherein the mixing weight ratio of the hydrophilic modified polypropylene compound and thermoplastic starch is 50:50 to 90:10.
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