CN114479388A - Biodegradable film blowing material capable of recycling reclaimed materials and preparation method thereof - Google Patents
Biodegradable film blowing material capable of recycling reclaimed materials and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 114
- 238000010096 film blowing Methods 0.000 title claims abstract description 54
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 70
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 59
- 239000004626 polylactic acid Substances 0.000 claims abstract description 59
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 13
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000012785 packaging film Substances 0.000 claims abstract description 6
- 229920006280 packaging film Polymers 0.000 claims abstract description 6
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002745 absorbent Effects 0.000 claims abstract description 5
- 239000002250 absorbent Substances 0.000 claims abstract description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001361 adipic acid Substances 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 229920001896 polybutyrate Polymers 0.000 claims abstract 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002699 waste material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 9
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 9
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 9
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- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
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- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 58
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
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- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000007791 dehumidification Methods 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940075529 glyceryl stearate Drugs 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- -1 polybutylene adipate terephthalate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- 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
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- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention discloses a biodegradable film blowing material capable of recycling reclaimed materials and a preparation method thereof, wherein the biodegradable film blowing material comprises the following raw materials in parts by mass: 2 to 7 parts of polylactic acid resin, 40 to 70 parts of poly-adipic acid/butylene terephthalate resin, 10 to 50 parts of recycled materials of degradable film bag products, 10 to 30 parts of calcium carbonate powder, 2 to 4 parts of lubricant, 1 to 4 parts of ultraviolet absorbent, 0.5 to 3 parts of antioxidant, 0.5 to 3 parts of glycidyl methacrylate, 0.3 to 1 part of styrene and 0.1 to 0.3 part of di-tert-butyl peroxide. The biodegradable film blowing material provided by the invention is added with the recycled material of the degradable film bag product to replace PLA/PBAT new material resin, so that the recycled material of the degradable film bag product is recycled, the cost is low, the industrial production is expected, and the biodegradable film blowing material can be widely applied to the fields of garbage bags, shopping bags, mulching films, industrial packaging films, bubble films and the like.
Description
Technical Field
The invention relates to the field of biodegradable film preparation, in particular to a biodegradable film blowing material capable of recycling reclaimed materials and a preparation method thereof.
Background
Under the east wind of the policy of 'plastic prohibition', the degradable material becomes a new favorite in the market. Therefore, the degradable material becomes the 'golden racetrack' which is competitive and incoming for many enterprises. However, the industrial and large-scale development of degradable materials is good, and due to the degradable materials such as polylactic acid resin (PLA), polybutylene adipate terephthalate (PBAT), PBS and the like, the cost problem is solved, and the substitution of large-area disposable consumables, hotel supplies, industrial packages and the like is limited.
In general, the demand for degradable materials is mainly concentrated in the packaging field, and soft packages and hard packages account for more than 50% of the total. Currently, the industry chain of degradable plastics has three major parts, namely design and application of key raw materials, degradable plastic products and degradable plastics. Among them, PLA and PBAT are the main development directions of degradable materials in the future.
At present, China Jilin province, Hainan province and Jiangsu province are all promoting biodegradable material markets, Hainan also recently establishes a law, products promoted by the local law are difficult to counterfeit due to strict supervision, but the cost is too high, the use amount is not large, and the waste post-treatment process still has no special specification. The use of disposable non-degradable plastic products is completely prohibited from using 1 month and 1 day of 2015 of Jilin province, the market capacity of the local disposable plastic products is 2 ten thousand tons, but after one year of plastic prohibition, the use amount of disposable biodegradable products is only 4000 tons.
For example, currently used mulching films use petroleum-based biodegradable materials PBAT. PLA is not made into mulching film. The cost of the mulching film made of PBAT is three times of that of the common PE mulching film. So to say, although 200 ten thousand tons of mulching films need to be replaced in China. There is still no good solution under cost pressure.
For another example, why can a device made of polylactic acid material not be recycled since it is strong and sturdy? Or the material is recycled and polymerized again to produce regenerated polylactic acid material, and is used on a large number of disposable appliances? The PLA resin can be recycled in the technology, but the recycling amount is small, and dehumidification drying or chain extension is needed in the recycling process, so the cost is high.
The pure PBAT blown film processing is unstable and difficult to be molded by normal blown film. Compared with a pure PBAT system, the film has high tensile modulus and increased tensile strength due to the introduction of PLA molecular chains. However, the PLA/PBAT physical blending is an incompatible two-phase system, especially the PLA/PBAT blending blown film material with the PLA content exceeding 8%, if no epoxy chain extender is used for system chain extension, the mechanical property of the film product is too poor to meet the application, so the biodegradable blown film grade modified material is the epoxy chain extender 4468 contacted with the Pasfu edible product, the price is too high, and the cost of the disposable plastic bag is too high. In the low-end film product modified material, a part of PBAT high-filling calcium carbonate is adopted to enhance and increase openings, and simultaneously, the cost is reduced, but excessive dispersant and lubricant are often added into the high-filling inorganic film, the VOC and the odor of the film exceed the standard, and the application is limited. The modulus is improved without PLA, the tensile strength is too low, the film stiffness is poor, the heat sealing strength is poor, and the water leakage of the prepared bag is unqualified. The elongation at break is too large, the amount of tensile deformation is too large, the bag is easy to deform, and the application is limited. The film has poor stiffness, the heat sealing is difficult to stabilize (the heat sealing is sticky, uneven and has high defective rate), so that more than 20 percent of waste is generated in the bag making process, and the cost of degraded products is increased indirectly.
The mixed system of PLA and PBAT is one of the common systems of the existing biodegradable blown film material, and 15-20% of reclaimed materials can be remained in the production process. The PLA/PBAT reclaimed materials are crushed and directly melted for granulation, which causes multiple times of high-temperature shearing, molecular weight reduction, serious decomposition and difficult film blowing.
Disclosure of Invention
The invention aims to provide a biodegradable film blowing material capable of recycling reclaimed materials and a preparation method thereof, and aims to solve the problem of compatibility of a new material and the reclaimed materials and improve melt strength so as to obtain a material with low cost, good performance and more stability.
The invention adopts the following technical scheme for realizing the purpose:
a biodegradable film blowing material capable of recycling reclaimed materials is characterized in that: the biodegradable film blowing material comprises the following raw materials in parts by mass: 2 to 7 parts of polylactic acid resin, 40 to 70 parts of poly-adipic acid/butylene terephthalate resin, 10 to 50 parts of recycled materials of degradable film bag products, 10 to 30 parts of calcium carbonate powder, 2 to 4 parts of lubricant, 1 to 4 parts of ultraviolet absorbent, 0.5 to 3 parts of antioxidant, 0.5 to 3 parts of glycidyl methacrylate, 0.3 to 1 part of styrene and 0.1 to 0.3 part of di-tert-butyl peroxide.
Further, the recycled material of the degradable film bag product is waste (also called recycled material) generated after a film blowing process of a marketable film blowing level film material system. The film system is a PLA/PBAT system, a PLA/PBAT/calcium carbonate system, or a PBAT/calcium carbonate system. The melt index of the recycled material of the degradable film bag product is 5-15 g/10min (190 ℃, 2.16 kg).
Further: the polylactic resin is in a blown film grade, has a melt index of 3-7 g/10min (190 ℃, 2.16kg), and can be at least one of LX175, L175, FY801 and FY 804; the poly (butylene adipate/terephthalate) resin is in a blown film grade, has a melt index of 3-5 g/10min (190 ℃, 2.16kg), and can be selected from at least one of TH801T and KHB21AP 11.
Further: the ultraviolet absorbent is at least one of benzophenones (such as 2-hydroxy-4-n-octoxybenzophenone, 2, 4-dihydroxybenzophenone), resorcinol monobenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and titanium dioxide; the calcium carbonate powder is nano calcium carbonate with the mesh number of 5000 meshes, 8000 meshes and the like; the antioxidant can be at least one of antioxidant 1010 and antioxidant 168; the lubricant is at least one of stearic acid (such as zinc stearate, calcium stearate, butyl stearate, glyceryl stearate) and oleamide.
Further, the biodegradable film blowing material preferably comprises the following raw materials in parts by mass: 3 parts of polylactic acid resin, 47 parts of poly-adipic acid/butylene terephthalate resin, 20 parts of a degradable film bag product reclaimed material, 30 parts of calcium carbonate powder, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate, 1.5 parts of 2-hydroxy-4-n-octyloxy benzophenone, 0.5-3 parts of glycidyl methacrylate, 0.3-1 part of styrene and 0.1-0.3 part of di-tert-butyl peroxide.
The preparation method of the biodegradable film blowing material comprises the following steps: drying and crushing reclaimed materials of the degradable film bag product, weighing the raw materials according to the proportion, adding the raw materials into a high-speed mixer for full mixing, and feeding the obtained mixture into a double-screw extruder for extrusion granulation to obtain a biodegradable film blowing material; and conveying the biodegradable film blowing material to a dryer for drying, and sending the material to a film blowing machine for film blowing and forming after determining that no heavy metal is left by a metal detector, thereby obtaining the biodegradable packaging film product.
The biodegradable film blowing material provided by the invention is added with the recycled material of the degradable film bag product to replace PLA/PBAT new material resin, so that the recycled material of the degradable film bag product is recycled, the modification efficiency is improved by adopting a free radical polymerization and ring-opening reaction integrated method, in a high-temperature shearing and extruding field, under the condition of a di-tert-butyl peroxide initiator, glycidyl methacrylate and styrene are subjected to free radical copolymerization to synthesize a polymer with an epoxy group, the epoxy group polymer reacts with terminal carboxyl groups of PLA and PBAT under the catalysis of zinc stearate, the styrene effectively improves the grafting rate of glycidyl methacrylate, more grafting points are endowed, the reaction efficiency is improved, the safety performance of small molecule migration is avoided, and the chain extension efficiency in PLA/PBAT is also obviously improved. The epoxy chain extender 4468 commonly used in blown film modified materials in the market is completely replaced, so that the problem of high cost of the existing biodegradable film bag products is well solved, and compared with the biodegradable film grade modified materials such as PLA/PBAT, PLA/PBAT/calcium carbonate, PLA/PBAT/starch, PLA/PBAT/talcum powder or PBAT/calcium carbonate, PBAT/starch, PBAT/talcum powder and the like commonly used in the market, the film bag product obtained by the invention has lower cost, is expected to be produced industrially and has good popularization and application prospects.
The waste materials of the degradable film bag products are subjected to primary double-screw melting shearing plasticizing granulation and single-screw melting high-pressure film blowing before being directly crushed, and then are subjected to secondary double-screw melting shearing plasticizing granulation and single-screw melting high-pressure film blowing, the broken chains of large molecular parts of PLA and PBAT are degraded, small molecules are increased, the fluidity is increased, the melt index is increased linearly, the high-pressure film blowing processing technology cannot be met, and the reason is that the high-temperature shearing is carried out for multiple times, the molecular weight is reduced, the decomposition is serious, and the film blowing is difficult. The invention uses the method of integrating free radical polymerization and ring-opening reaction to solve the compatibility between the degraded recycled material and the new degraded material, so that the compatibility between the PLA and the PBAT interface after chain extension is obviously improved, the PLA/PBAT melt strength is high, the requirement of film blowing processing is met, and the biodegradable material with lower product cost and stable comprehensive performance is obtained.
Compared with the prior art, the invention has the beneficial effects that:
1. the formula system of the invention greatly reduces the cost of the existing biodegradable material, achieves the LDPE cost advantage, improves the market popularization easiness of the biodegradable material, has higher use value, and brings greater economic and social benefits by popularization and application. The biodegradable film blowing material can be widely used in the fields of garbage bags, shopping bags, mulching films, industrial packaging films, bubble films, hand bags and the like.
2. The formula system of the invention has the following characteristics: original strength and toughness can be maintained; having sufficient viscoelasticity to stretch the wrapped film for a sufficient amount of time without sagging; good stretchability.
3. Compared with a system without adding the recycled material of the degradable film bag product, the biodegradable film stretched longitudinally has the following characteristics: the strength retention rate is 100%, the transparency and the surface gloss are not influenced, and the use value of the product is improved; the melt strength of the recycled blend is high, the thickness of the biodegradable film can be reduced, the width of the biodegradable film can be increased, and the cost is greatly reduced.
4. The method realizes the recycling of the reclaimed materials of the degradable membrane bag products, has simple process, environmental protection and low cost, is expected to realize industrial production, and has good popularization and application prospects.
Drawings
FIG. 1 is a photograph of a shopping bag processed using the biodegradable blown film of example 1 of the present invention;
FIG. 2 is an SEM image of a shopping bag processed by using the biodegradable blown film material of example 1 of the present invention;
FIG. 3 is an SEM image of a shopping bag processed by using the biodegradable blown film of comparative example 1 of the present invention;
FIG. 4 is an SEM image of a shopping bag processed by using the biodegradable blown film of comparative example 2 of the present invention;
FIG. 5 is an SEM image of a shopping bag processed by using the biodegradable blown film of comparative example 3 of the present invention.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
The recycled material of the degradable film bag product used in the following examples is the film blowing waste material of a PLA/PBAT/calcium carbonate film material system, and the melt index of the recycled material is 12.3g/10 min. Drying the PLA/PBAT/calcium carbonate film blowing waste for 2 hours at 80 ℃, and crushing the waste into 200 meshes by using a crusher for later use.
Example 1
The biodegradable film blowing material comprises the following raw materials in parts by mass: 3 parts of PLA, 47 parts of PBAT, 20 parts of PLA/PBAT/calcium carbonate blown film waste, 30 parts of calcium carbonate powder, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate, 1.5 parts of 2-hydroxy-4-n-octoxy benzophenone, 2.2 parts of glycidyl methacrylate, 0.6 part of styrene and 0.15 part of di-tert-butyl peroxide.
Example 2
The biodegradable film blowing material comprises the following raw materials in parts by mass: 3 parts of PLA, 47 parts of PBAT, 20 parts of PLA/PBAT/calcium carbonate blown film waste, 30 parts of calcium carbonate powder, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate, 1.5 parts of 2-hydroxy-4-n-octoxy benzophenone, 1 part of glycidyl methacrylate, 0.3 part of styrene and 0.1 part of di-tert-butyl peroxide.
Example 3
The biodegradable film blowing material comprises the following raw materials in parts by mass: 3 parts of PLA, 47 parts of PBAT, 20 parts of PLA/PBAT/calcium carbonate blown film waste, 30 parts of calcium carbonate powder, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate, 1.5 parts of 2-hydroxy-4-n-octoxy benzophenone, 3 parts of glycidyl methacrylate, 0.5 part of styrene and 0.15 part of di-tert-butyl peroxide.
Example 4
The biodegradable film blowing material comprises the following raw materials in parts by mass: 3 parts of PLA, 47 parts of PBAT, 20 parts of PLA/PBAT/calcium carbonate blown film waste, 30 parts of calcium carbonate powder, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate, 1.5 parts of 2-hydroxy-4-n-octoxy benzophenone, 2.2 parts of glycidyl methacrylate and 0.15 part of di-tert-butyl peroxide.
Comparative example 1
The biodegradable film blowing material comprises the following raw materials in parts by mass: 3 parts of PLA, 47 parts of PBAT, 20 parts of PLA/PBAT/calcium carbonate blown film waste, 30 parts of calcium carbonate powder, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate and 1.5 parts of 2-hydroxy-4-n-octyloxybenzophenone.
Comparative example 2
The raw material of the biodegradable film blowing material of the comparative example adopts 100 parts of PLA/PBAT/calcium carbonate film blowing waste.
Comparative example 3
The biodegradable film blowing material comprises the following raw materials in parts by mass: 100 parts of PLA/PBAT/calcium carbonate blown film waste, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate, 1.5 parts of 2-hydroxy-4-n-octoxy benzophenone, 2.2 parts of glycidyl methacrylate, 0.6 part of styrene and 0.15 part of di-tert-butyl peroxide.
In order to test the performance of the biodegradable packaging film materials in examples 1 to 4 and comparative examples 1 to 3, the biodegradable packaging film materials were processed into biodegradable shopping bags (490mm × (300+80) mm × 0.025mm) as follows: adding PLA, PBAT, PLA/PBAT/calcium carbonate film blowing waste materials into a high-speed mixer, fully mixing (the speed is 500r/min, the time is 6min), adding glycidyl methacrylate, styrene and di-tert-butyl peroxide, uniformly mixing (the speed is 500r/min, the time is 6min), then adding a lubricating agent, an ultraviolet absorbent, an antioxidant and calcium carbonate powder, and mixing and stirring (the speed is 500r/min, the time is 6 min). And (3) conveying the obtained mixture into a double-screw extruder for extrusion granulation (the temperature of the double-screw extruder is 165-.
The films obtained in examples 1 to 4 and comparative examples 1 to 3 were tested for machine direction tensile strength, transverse direction tensile strength, dart impact, water leakage and seal strength in accordance with GB/T1040.2-2006, GB/T38082-2019, and the results are shown in Table 1.
TABLE 1
The experimental results in table 1 show that the biodegradable film prepared by using the film blowing material of embodiments 1-4 of the present invention has good puncture strength, tensile strength, elongation at break, improved tear resistance and improved heat sealing, and can meet the use requirements of shopping bags, garbage bags, bubble films, agricultural mulching films and biodegradable film materials for industrial packaging.
FIG. 3 is a SEM image of a shopping bag processed by using the biodegradable film blowing material of comparative example 1, after a large amount of PLA/PBAT/calcium carbonate film bag crushed material is added into a PLA/PBAT blending system, the PLA/PBAT/calcium carbonate film bag crushed material is subjected to secondary melting processing to cause partial degradation, and no molecular chain extension is introduced, so that the PLA/PBAT blending system has large microscopic particles, poor dispersion and obvious phase separation of two phases, namely poor interface compatibility. FIG. 4 is an SEM image of a shopping bag processed by using the biodegradable blown film material of comparative example 2 of the present invention, wherein the broken material of the PLA/PBAT/calcium carbonate film bag has more micro-large particles and poor dispersion in the secondary melting process. FIG. 5 is an SEM image of a shopping bag processed by using the biodegradable blown film material of comparative example 3, and a comparison shows that after a large amount of broken PLA/PBAT/calcium carbonate film bag materials are added into a PLA/PBAT blending system, the PLA/PBAT blending system introduces molecular chain extension, the compatibility of the PLA/PBAT blending system is remarkably improved, microscopic large particles are obviously reduced, and the dispersion is improved. Fig. 2 is an SEM image of a shopping bag processed by using the biodegradable blown film material of example 1 of the present invention, wherein a PLA/PBAT blend system is added with not only a PLA/PBAT/calcium carbonate bag crushed material but also a molecular chain extension, the PLA/PBAT blend system is microscopically present, almost no particles are present, and the dispersibility is excellent. And the PLA/PBAT blending system has good interface compatibility, so the compatibility of the PLA/PBAT blending system is obviously improved by adding molecular chain extension, and the physical property of the product is greatly improved.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The utility model provides a cyclic utilization reclaimed materials's biodegradable blows membrane material which characterized in that: the biodegradable film blowing material comprises the following raw materials in parts by mass: 2 to 7 parts of polylactic acid resin, 40 to 70 parts of poly-adipic acid/butylene terephthalate resin, 10 to 50 parts of recycled materials of degradable film bag products, 10 to 30 parts of calcium carbonate powder, 2 to 4 parts of lubricant, 1 to 4 parts of ultraviolet absorbent, 0.5 to 3 parts of antioxidant, 0.5 to 3 parts of glycidyl methacrylate, 0.3 to 1 part of styrene and 0.1 to 0.3 part of di-tert-butyl peroxide.
2. The biodegradable film blowing material capable of recycling recycled materials as claimed in claim 1, wherein: the recycled material of the degradable film bag product is waste material generated after a film blowing processing of a marketable film blowing level film material system.
3. The biodegradable film blowing material capable of recycling recycled materials as claimed in claim 2, wherein: the film system is a PLA/PBAT system, a PLA/PBAT/calcium carbonate system, or a PBAT/calcium carbonate system.
4. The biodegradable film blowing material capable of recycling recycled materials according to claim 2 or 3, which is characterized in that: the melt index of the recycled material of the degradable film bag product is 5-15 g/10 min.
5. The biodegradable film blowing material capable of recycling recycled materials as claimed in claim 1, wherein: the polylactic resin is in a film blowing grade, and the melt index is 3-7 g/10 min; the poly (butylene adipate/terephthalate) resin is in a blown film grade, and the melt index is 3-5 g/10 min.
6. The biodegradable film blowing material capable of recycling recycled materials as claimed in claim 1, wherein: the biodegradable film blowing material comprises the following raw materials in parts by mass: 3 parts of polylactic acid resin, 47 parts of poly-adipic acid/butylene terephthalate resin, 20 parts of a degradable film bag product reclaimed material, 30 parts of calcium carbonate powder, 0.4 part of antioxidant 1010, 1.2 parts of antioxidant 168, 1 part of oleamide, 1 part of zinc stearate, 1.5 parts of 2-hydroxy-4-n-octyloxy benzophenone, 0.5-3 parts of glycidyl methacrylate, 0.3-1 part of styrene and 0.1-0.3 part of di-tert-butyl peroxide. .
7. A preparation method of the biodegradable film blowing material as set forth in any one of claims 1 to 6, characterized in that:
drying and crushing reclaimed materials of the degradable film bag product, weighing the raw materials according to the proportion, adding the raw materials into a high-speed mixer for full mixing, and feeding the obtained mixture into a double-screw extruder for extrusion granulation to obtain a biodegradable film blowing material; and conveying the biodegradable film blowing material to a dryer for drying, and sending the material to a film blowing machine for film blowing and forming after determining that no heavy metal is left by a metal detector, thereby obtaining the biodegradable packaging film product.
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