CN114437523A - Biodegradable high-temperature-resistant polylactic acid straw and preparation method thereof - Google Patents
Biodegradable high-temperature-resistant polylactic acid straw and preparation method thereof Download PDFInfo
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- CN114437523A CN114437523A CN202210224645.8A CN202210224645A CN114437523A CN 114437523 A CN114437523 A CN 114437523A CN 202210224645 A CN202210224645 A CN 202210224645A CN 114437523 A CN114437523 A CN 114437523A
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- polylactic acid
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- resistant polylactic
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- 239000010902 straw Substances 0.000 title claims abstract description 60
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 37
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 41
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 40
- 239000007822 coupling agent Substances 0.000 claims abstract description 33
- 239000004970 Chain extender Substances 0.000 claims abstract description 29
- 239000000945 filler Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 16
- 235000012424 soybean oil Nutrition 0.000 claims description 15
- 239000003549 soybean oil Substances 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 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
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 22
- 238000002425 crystallisation Methods 0.000 abstract description 18
- 230000008025 crystallization Effects 0.000 abstract description 18
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 8
- 238000000137 annealing Methods 0.000 abstract description 7
- 239000002667 nucleating agent Substances 0.000 abstract description 7
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000001185 bone marrow Anatomy 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention relates to the technical field of polylactic acid materials, and provides a biodegradable high-temperature-resistant polylactic acid straw which comprises the following components in parts by weight: 1-50 parts of PLLA, 50-95 parts of PBS, 0.01-10 parts of a compatilizer, 0.01-5 parts of a dispersant, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-50 parts of a filler. Wherein the compatilizer promotes the compatibility among the raw materials; in the extrusion forming process of PLLA, quasi-orthorhombic crystals and orthorhombic crystals are generated during crystallization; PBS in the raw material can be used as a PLLA nucleating agent, so that the crystallization rate is improved, further, annealing is not needed for further crystallization, and the preparation process is simplified; meanwhile, the crystal structure of the straw can be optimized, and the heat resistance of the straw is further improved.
Description
Technical Field
The invention relates to the technical field of polylactic acid materials, in particular to a biodegradable high-temperature-resistant polylactic acid straw and a preparation method thereof.
Background
The straw is a cylindrical hollow plastic product, and is mainly used for drinking beverages in cups and also for sucking bone marrow of long bones of cooked animals.
The raw materials of the biodegradable high temperature resistant polylactic acid straw provided by the prior art usually consist of polylactic acid (PLA), poly adipic acid/polybutylene terephthalate (PBAT), a dispersant, a plasticizer, a coupling agent, a chain extender and a filler.
When the straw is prepared by adopting the raw materials, annealing treatment is needed after extrusion forming, so that the high temperature resistance of the straw is improved.
Disclosure of Invention
The invention aims to provide a biodegradable high-temperature-resistant polylactic acid straw which can be obtained without annealing treatment.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a biodegradable high-temperature-resistant polylactic acid straw which comprises the following components in parts by weight: 1-50 parts of PLLA, 50-95 parts of PBS, 0.01-10 parts of a compatilizer, 0.01-5 parts of a dispersant, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-50 parts of a filler;
the compatilizer is at least one of PBST-g-GMA, PBST-g-MHA and PBAT-g-MAH.
Preferably, the weight average molecular weight of the PLLA is 30000-3000000, and the molecular weight distribution is 1.5-5.
Preferably, the weight average molecular weight of the PBS is 20000-130000, and the molecular weight distribution is 1.5-4.
Preferably, the dispersant comprises at least one of calcium stearate, ethylene bis stearamide paraffin wax and polyethylene wax.
Preferably, the plasticizer includes at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride.
Preferably, the coupling agent comprises at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum titanate coupling agent.
Preferably, the chain extender includes a polyurethane chain extender and/or an epoxy chain extender.
Preferably, the polyurethane chain extender comprises ADR4375 and/or ADR 4400; the epoxy chain extender comprises CE1105 and/or 3525G.
Preferably, the filler comprises at least one of calcium carbonate, montmorillonite, mica powder and talc.
The scheme also provides a preparation method of the biodegradable heat-resistant polylactic acid straw, which comprises the steps of granulating, melting, mixing and extruding in sequence; the extrusion is not annealed.
The invention provides a biodegradable high-temperature-resistant polylactic acid straw, which promotes the compatibility among raw materials by adding a compatilizer into the raw materials, thereby improving the impact property of a notch of the straw; by selecting PLLA as a raw material, in the extrusion forming process, the PLLA can generate quasi-orthorhombic crystals and orthorhombic crystals during crystallization; PBS is added into the raw materials and can be used as a PLLA nucleating agent, so that the crystallization rate is improved, further, the annealing is not needed for further crystallization, and the preparation process is simplified; meanwhile, the crystal structure of the straw can be optimized, and the heat resistance of the straw is further improved. The experiment result shows that the impact property of the notch of the straw obtained by the technical scheme provided by the invention is not lower than 5KJ/m2And simultaneously the Vicat temperature is not lower than 75 ℃.
Detailed Description
The invention provides a biodegradable high-temperature-resistant polylactic acid straw which comprises the following components in parts by weight: 1-50 parts of PLLA, 50-95 parts of PBS, 0.01-10 parts of a compatilizer, 0.01-5 parts of a dispersant, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-50 parts of a filler.
The biodegradable high-temperature-resistant polylactic acid straw comprises, by weight, 1-50 parts of PLLA, preferably 5-40 parts of PLLA, and more preferably 10-30 parts of PLLA. In the present invention, the PLLA represents poly-l-lactic acid. In the extrusion forming process, PLLA can generate quasi-orthorhombic crystals and orthorhombic crystals during crystallization; by selecting a specific substance as a nucleating agent, under the action of the nucleating agent, quasi-orthorhombic crystals and orthorhombic crystals formed by PLLA are further subjected to stereocomplex to generate a more stable crystal structure, namely a stereocomplex, and the complex forms triangular crystal nuclei at the initial stage of crystallization and has a unique crystallization mode, so that the material performance is more stable.
In the invention, the weight average molecular weight of the PLLA is preferably 30000-3000000, more preferably 20000-130000; the molecular weight distribution is preferably 1.5 to 5, more preferably 2 to 4. The weight average molecular weight of the PLLA is controlled in the range, so that the problems that the molecular weight is too small, the fluidity of the material is greatly changed in the processing process and the toughness of the material is influenced are avoided; the molecular weight is too high, and the melting of the material is difficult; and the PLLA within the molecular weight range is proper in price, so that the cost of the straw is reduced. By controlling the molecular weight distribution in the above range, the PLLA performance is stable.
The source of the PLLA is not specifically defined in the present invention, and conventional commercial products well known to those skilled in the art may be used. In the embodiment of the invention, the PLLA is an LX575 type PLLA. In an actual production factory, LXL in the LX575 represents low optical rotation.
The biodegradable high-temperature-resistant polylactic acid straw comprises 50-95 parts of PBS (poly butylenes succinate), preferably 55-80 parts of the PBS, by weight of 1-50 parts of PLLA. In the present invention, the PBS represents a copolymer of aliphatic diol 1, 4-Butanediol (BDO) and aliphatic diacid 1, 4-Succinic Acid (SA). In the invention, the PBS has better ductility and elongation at break, and also has better heat resistance and impact resistance; in addition, the composite material has excellent biodegradability, can be used as a PLLA nucleating agent, improves the crystallization rate, further does not need annealing for further crystallization, and can obtain a high-temperature-resistant straw.
The biodegradable high-temperature-resistant polylactic acid straw comprises, by weight of 1-50 parts of PLLA, 0.01-10 parts of a compatilizer, preferably 1-9 parts of the compatilizer, and more preferably 5-8 parts of the compatilizer. In the invention, the compatilizer can promote the compatibility among the raw materials, thereby improving the notch impact performance of the straw.
In the present invention, the compatibilizer is at least one of PBST-g-GMA, PBST-g-MHA and PBAT-g-MAH, preferably PBST-g-GMA. In the invention, PBST-g-GMA represents polybutylene succinate-butylene terephthalate grafted glycidyl methacrylate, PBST-g-MHA represents polybutylene succinate-butylene terephthalate grafted maleic anhydride, and PBAT-g-MAH represents polybutylene adipate/butylene terephthalate grafted maleic anhydride. In the invention, the PBST-g-GMA graft has the advantages of high grafting efficiency, short polymer synthesis time and the like, and is relatively low in price.
The source of the compatibilizer is not particularly specified in the invention, and the compatibilizer can be prepared by a preparation method well known to a person skilled in the art or a commercially available product can be directly purchased.
The biodegradable high-temperature-resistant polylactic acid straw comprises, by weight of 1-50 parts of PLLA, 0.01-5 parts of a dispersing agent, preferably 0.1-1 part, and more preferably 0.3-0.5 part. In the present invention, the dispersant can uniformly disperse inorganic and organic solid and liquid particles which are difficult to dissolve in liquid, and can prevent the particles from settling and coagulating to form a stable suspension.
In the present invention, the dispersant preferably includes at least one of calcium stearate, ethylene bis stearamide and polyethylene wax, preferably ethylene bis stearamide, i.e., EBS. In the invention, the ethylene bis stearamide has low odor and low addition content, has the function of internal and external lubrication, and can be used as the dispersant to obtain the straw with better comprehensive performance.
The source of the dispersant is not particularly specified in the present invention, and the dispersant can be prepared by a preparation method well known to those skilled in the art or a commercially available product can be directly purchased.
The biodegradable high-temperature-resistant polylactic acid straw comprises, by weight of 1-50 parts of PLLA, 0.01-5 parts of a plasticizer, preferably 0.1-3 parts, and more preferably 0.5-1 part. In the invention, the plasticizer can reduce intermolecular force, so that the viscosity of the polymer is reduced, and the flexibility is enhanced.
In the present invention, the plasticizer preferably includes at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride, and more preferably epoxidized soybean oil. In the invention, the epoxy group of the epoxy soybean oil has reactivity with the group resin PLLA, so that the comprehensive performance of the obtained straw material can be further improved.
The source of the plasticizer is not particularly specified in the present invention, and the plasticizer can be prepared by a preparation method known to those skilled in the art or a commercially available product can be directly purchased.
The biodegradable high-temperature-resistant polylactic acid straw comprises 1-50 parts by weight of a filler, preferably 5-30 parts by weight of the filler, and more preferably 10-25 parts by weight of PLLA. In the present invention, the filler may enhance the overall performance of the polymeric material.
In the present invention, the filler preferably includes at least one of calcium carbonate, montmorillonite, mica powder, and talc. In the present invention, the particle diameter D of the filler50Preferably 1.2 to 3 μm. The particle size of the filler is controlled within the range, so that the dispersion uniformity of the filler in the raw materials can be improved, and the mechanical property of the material is improved; meanwhile, the increase of the production cost caused by the over-small particle size is avoided, so that the raw material cost for producing the straw is reduced.
The source of the filler is not specifically defined in the present invention, and a commercially available product well known to those skilled in the art may be used.
The biodegradable high-temperature-resistant polylactic acid straw comprises, by weight, 1-50 parts of a filler, 0.01-5 parts of a coupling agent, preferably 0.05-0.3 part of a coupling agent, and more preferably 0.1-0.25 part of a coupling agent.
In the present invention, the coupling agent preferably includes at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum-titanium ester coupling agent, and more preferably an aluminum-titanium ester coupling agent. The aluminum titanate coupling agent is used as the coupling agent of the invention, and is easier to be dispersed uniformly in a raw material system.
The source of the coupling agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
The biodegradable high-temperature-resistant polylactic acid straw comprises, by weight of 1-50 parts of PLLA, 0.01-5 parts of a chain extender, preferably 0.1-1 part, and more preferably 0.3-0.5 part. In the invention, the chain extender can react with the polymer in the raw material, so that the molecular weight of the polymer is improved, and the mechanical property of the material is further improved.
In the present invention, the chain extender preferably includes a polyurethane chain extender and/or an epoxy chain extender, and the polyurethane chain extender preferably includes ADR4375 and/or ADR 4400; the epoxy chain extender preferably includes CE1105 and/or 3525G. The chain extender is selected as the chain extender of the technical scheme of the invention, so that the polymer with proper polymerization degree can be more easily obtained, and the optimal comprehensive performance of the material can be realized due to the proper polymerization degree of the obtained polymer material.
The source of the chain extender is not particularly specified in the present invention, and commercially available products well known to those skilled in the art may be used.
The preparation method of the biodegradable heat-resistant polylactic acid straw comprises the steps of granulating, melting, mixing and extruding in sequence; the extrusion is not annealed. PBS in the raw materials in the technical scheme provided by the invention can be used as a PLLA nucleating agent, so that the crystallization rate is improved, further, the further crystallization is not required to be performed by annealing, and the preparation process is simplified.
In the present invention, the method for preparing the biodegradable polylactic acid straw preferably comprises: and mixing the PLLA, the PBS, the compatilizer, the coupling agent, the chain extender, the dispersant, the filler and the plasticizer, and then sequentially granulating, drying and extruding and forming to obtain the biodegradable heat-resistant polylactic acid straw.
In the present invention, the PLLA, PBS, the compatibilizer, and the filler are preferably dried before mixing. The drying method is not particularly limited in the present invention, and the moisture in the raw materials may be removed by a drying method known to those skilled in the art. The invention dries the raw materials in advance, and can avoid the influence of moisture in the raw materials on the granulation process, thereby reducing the performance of the straw.
According to the invention, preferably, the coupling agent and the filler are mixed to obtain the activated filler, then the activated filler is mixed with PLLA, PBS, the compatilizer, the chain extender, the dispersant and the plasticizer, and then granulation is carried out. The invention is beneficial to improving the dispersibility of the filler in the formula by activating the filler by using the coupling agent in advance.
In the present invention, the apparatus for granulation is preferably a twin-screw extruder. The granulation mode is not specially specified in the invention, and the granules can be obtained by adopting a granulation mode known by a person skilled in the art and utilizing a double-screw extruder for granulation. The raw materials are granulated, so that the dispersibility among the raw materials is improved in the later extrusion forming process, and the comprehensive performance of the straw is improved.
In the present invention, the temperature of each part of the twin-screw extruder is preferably: 150 ℃ in the first zone, 160 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the fourth zone, 170 ℃ in the fifth zone, 175 ℃ in the sixth zone and 180 ℃ in the machine head; the screw rotating speed of the double-screw extruder is preferably 60-600 rpm, more preferably 100-500 rpm, and most preferably 200-300 rpm; the length-diameter ratio L/D of the screw of the double-screw extruder is preferably (40-100): 1, and more preferably 80: 1. According to the invention, all process parameters of the double-screw extruder are limited within the ranges, and the obtained straw has good comprehensive performance.
The drying method after granulation is not particularly specified in the present invention, and the granules prepared after granulation are dried by a drying method well known to those skilled in the art, and the moisture in the granules during granulation is removed.
In the invention, the extrusion forming device is a single-screw extruder. The extrusion forming operation is not specially specified in the invention, and the straw is prepared by adopting the extrusion forming operation known by the technical personnel in the field and utilizing a single-screw extruder.
In the present invention, the temperature of each part of the single screw extruder is preferably: 160 ℃ in the first area, 170 ℃ in the second area, 180 ℃ in the third area, 190 ℃ in the fourth area and 205 ℃ in a machine head; the screw rotating speed of the single-screw extruder is preferably 100-400 rpm, and more preferably 200-300 rpm; the speed of the single-screw extruder for pulling the pipe blank by the pulling equipment is 0.5-1.5 m/s, and more preferably 1 m/s. The water cooling temperature of the water cooling device of the single-screw extruder is preferably 30-50 ℃, and more preferably 40 ℃. The invention limits the technological parameters of each part of the single screw extruder in the above range, and the obtained straw has good comprehensive performance.
The invention provides a biodegradable high-temperature-resistant polylactic acid straw which comprises the following components in parts by weight: 1-50 parts of PLLA, 50-95 parts of PBS, 0.01-10 parts of a compatilizer, 0.01-5 parts of a dispersant, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-50 parts of a filler. Wherein the compatilizer promotes the compatibility among the raw materials; in the extrusion forming process of PLLA, quasi-orthorhombic crystals and orthorhombic crystals are generated during crystallization; PBS in the raw material can be used as a PLLA nucleating agent, so that the crystallization rate is improved, further, annealing is not needed for further crystallization, and the preparation process is simplified; meanwhile, the crystal structure of the straw can be optimized, and the heat resistance of the straw is further improved.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the examples, the specific specification or abbreviation of the raw materials is as follows: PLLA (designation LX575, weight average molecular weight 207000g/mol, molecular weight distribution 1.8; designation LX175, weight average molecular weight 207000g/mol, molecular weight distribution 1.8), PBS (designation TH803s, weight average molecular weight 68000, molecular weight distribution 2.2), compatibilizer: PBST-g-GMA (brand)Number FL-02), filler: nano calcium carbonate (trade name XF-10, particle diameter D)501.2 μm) or filler mica powder (trade name YMF06, particle diameter D)501.2 μm) or talc (trade name HTP05L, particle size D)501.2 μm), coupling agent: aluminum-titanium coupling agent, plasticizer: epoxidized soybean oil, chain extender: ADR-4400, dispersant: ethylene bis stearamide, EBS for short
Example 1
The components and the dosage are as follows: 20 parts of LX575, 55 parts of TH803s, 5 parts of PBST-g-GMA, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated XF-10.
Pretreatment: (1) drying LX575, PBS and PBST-g-GMA in a blast oven at 80 ℃ for 4 h; XF-10 is dried in a 105 ℃ blast oven for 4 h.
(2) 99 parts of nano calcium carbonate and 1 part of aluminum-titanium coupling agent are stirred for 5 minutes at 90 ℃ to obtain the activated XF-10.
The preparation method comprises the following specific steps:
(I) mixing the LX575, TH803S, PBST-g-GMA and 0.8 part of epoxy soybean oil in parts by weight for 3min, then sequentially adding ADR-4400, EBS and 20 parts of activated XF-10, and mixing at normal temperature for 8min in a high-speed mixer to obtain a mixture;
(II) adding the mixture obtained in the step (I) into a double-screw machine for extrusion and granulation to obtain granules; the temperature of each zone of the double-screw machine is as follows: 150 ℃ in the first zone, 160 ℃ in the second zone, 160 ℃ in the third zone, 170 ℃ in the fourth zone, 170 ℃ in the fifth zone, 175 ℃ in the sixth zone and 180 ℃ in the machine head; the rotating speed of the screw is 200rpm, and the length-diameter ratio L/D is 80/1;
(III) drying the granules obtained in the step (II) in a forced air oven at 80 ℃ for 4 hours to obtain dried granules;
(IV) adding the dried granules obtained in the step (III) into a single-screw extruder for extrusion to obtain the biodegradable polylactic acid heat-resistant straw, wherein the temperature of each area of the single-screw extruder is as follows: the method comprises the steps of firstly, 150 ℃, secondly, 170 ℃, thirdly, 180 ℃, fourthly, 190 ℃, 205 ℃, the rotating speed of a screw is 200-300 rpm, the speed of a traction device for drawing a pipe blank is 1 m/s, and the water cooling temperature of a water cooling device is 40 ℃ to obtain the suction pipe.
Example 2
The procedure was the same as in example 1, except that: the filler was changed to talc HTP05L, and the same procedure was carried out by drying talc in a 105 ℃ forced air oven for 4 hours and stirring the dried talc with 1 part of an aluminum-titanium coupling agent for 5 minutes at 90 ℃ to give activated HTP 05L.
The components and the dosage are as follows: 20 parts LX575, 55 parts TH803s, 5 parts PBST-g-GMA, 0.8 parts epoxidized soybean oil, 0.4 parts ADR-4400, 0.5 parts EBS and 20 parts activated HTP 05L.
Example 3
The procedure was the same as in example 1, except that: the filler is changed into mica powder, the mica powder is dried in a 105 ℃ blast oven for 4 hours, and the dried mica powder and 1 part of aluminum-titanium coupling agent are stirred for 5 minutes at 90 ℃ to obtain the activated YMF 06.
The components and the dosage are as follows: 20 parts of LX575, 55 parts of TH803s, 5 parts of PBST-g-GMA, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated YMF 06.
Example 4
The procedure was the same as in example 3, except that: the components and the dosage are as follows: 20 parts LX575, 65 parts TH803s, 5 parts PBST-g-GMA, 0.8 parts epoxidized soybean oil, 0.4 parts ADR-4400, 0.5 parts EBS and 20 parts activated YMF 06.
Example 5
The procedure was the same as in example 3, except that: the components and the dosage are as follows: 20 parts LX575, 55 parts TH803s, 5 parts PBST-g-GMA, 0.8 parts epoxidized soybean oil, 0.4 parts ADR-4400, 0.5 parts EBS and 25 parts activated YMF 06.
Example 6
The procedure was the same as in example 3, except that: the components and the dosage are as follows: 20 parts of LX575, 55 parts of TH803s, 8 parts of PBST-g-GMA, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated YMF 06.
Comparative example 1
The procedure was the same as in example 3, except that: the components and the dosage are as follows: 50 parts of LX575, 25 parts of TH803S, 5 parts of PBST-g-GMA, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated YMF 06.
Comparative example 2
The procedure was the same as in example 3, except that: the components and the dosage are as follows: 20 parts of LX175, 55 parts of TH803s, 5 parts of PBST-g-GMA, 0.8 part of epoxidized soybean oil, 0.4 part of ADR-4400, 0.5 part of EBS and 20 parts of activated YMF 06.
Performance tests were performed on the straws prepared in examples 1 to 6 and comparative examples 1 to 2, and the test results are shown in Table 1.
And (4) testing standard: the notch impact is according to GB/T1843-2008, 1 type; tensile strength GB/T1040.2-2006, type 1A; bending strength GB/T9341-; the Vicat softening temperature is in accordance with GB/T1633-2000.
TABLE 1 Performance test results for straws prepared in examples 1-6 and comparative examples 1-2
From the results in table 1, it can be seen that the PBS in the system can well increase the heat-resistant temperature of the heat-resistant straw, and the larger the number of the system, the higher the heat-resistant temperature. It can be seen from comparative example 1 that the PBS content of the system is reduced, with the consequent deterioration of the crystallization properties of the composite material, resulting in a reduction of the heat-resistant temperature of the straw material. The change of the optical purity of PLA influences the change of the crystallization performance of the system, the material with high optical purity is better in heat resistance; the content of the compatilizer influences the compatibility of PLA and matrix resin, simultaneously, the notch impact strength of the composite material can be well improved, the stability of the straw material during extrusion is ensured, the blowing ratio is good, the content of the compatilizer is not too high, the heat-resistant temperature of the material can be influenced, and the mica powder in the three fillers has an obvious help effect on the heat-resistant temperature of a system.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A biodegradable high-temperature-resistant polylactic acid straw comprises the following components in parts by weight: 1-50 parts of PLLA, 50-95 parts of PBS, 0.01-10 parts of a compatilizer, 0.01-5 parts of a dispersant, 0.01-5 parts of a plasticizer, 0.01-5 parts of a coupling agent, 0.01-5 parts of a chain extender and 1-50 parts of a filler;
the compatilizer is at least one of PBST-g-GMA, PBST-g-MHA and PBAT-g-MAH.
2. The biodegradable high-temperature-resistant polylactic acid straw as claimed in claim 1, wherein the weight average molecular weight of the PLLA is 30000-3000000, and the molecular weight distribution is 1.5-5.
3. The biodegradable heat-resistant polylactic acid straw as claimed in claim 1, wherein the weight average molecular weight of the PBS is 20000 to 130000, and the molecular weight distribution is 1.5 to 4.
4. The biodegradable, high temperature resistant polylactic acid straw as claimed in claim 1, wherein said dispersing agent comprises at least one of calcium stearate, ethylene bis stearamide paraffin wax and polyethylene wax.
5. The biodegradable high temperature resistant polylactic acid straw according to claim 1, wherein the plasticizer comprises at least one of epoxidized soybean oil, polyethylene glycol, acetyl tributyl citrate, and acetylated monoglyceride fatty acid ester.
6. The biodegradable high temperature resistant polylactic acid straw according to claim 1, wherein the coupling agent comprises at least one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, and an aluminum-titanium ester coupling agent.
7. The biodegradable high temperature resistant polylactic acid straw according to claim 1, wherein the chain extender comprises a polyurethane chain extender and/or an epoxy chain extender.
8. The biodegradable, high temperature resistant polylactic acid straw according to claim 8, wherein the polyurethane chain extender comprises ADR4375 and/or ADR 4400; the epoxy chain extender comprises CE1105 and/or 3525G.
9. The biodegradable, high temperature resistant polylactic acid straw as claimed in claim 1, wherein the filler comprises at least one of calcium carbonate, montmorillonite, mica powder and talc.
10. The method for preparing the biodegradable high-temperature-resistant polylactic acid straw as claimed in any one of claims 1 to 9, which comprises the steps of granulating, melting, mixing and extrusion forming in sequence; the extrusion is not annealed.
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