CN112048783A - Biodegradable brush wire and preparation method thereof - Google Patents
Biodegradable brush wire and preparation method thereof Download PDFInfo
- Publication number
- CN112048783A CN112048783A CN202010935837.0A CN202010935837A CN112048783A CN 112048783 A CN112048783 A CN 112048783A CN 202010935837 A CN202010935837 A CN 202010935837A CN 112048783 A CN112048783 A CN 112048783A
- Authority
- CN
- China
- Prior art keywords
- treatment
- biodegradable
- polylactic acid
- brush
- brush wire
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000004626 polylactic acid Substances 0.000 claims abstract description 50
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 48
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009998 heat setting Methods 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 5
- -1 polybutylene succinate Polymers 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000004804 winding Methods 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 229930182843 D-Lactic acid Natural products 0.000 claims description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229940022769 d- lactic acid Drugs 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 2
- 239000004631 polybutylene succinate Substances 0.000 claims description 2
- 229920002961 polybutylene succinate Polymers 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 5
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 abstract 1
- 229920001896 polybutyrate Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- NQZRDXDTNFGVMK-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCC(=O)OCCCCO1 NQZRDXDTNFGVMK-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 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 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 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 group 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 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 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 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 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 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
- A46D1/04—Preparing bristles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/04—Melting filament-forming substances
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
- D02J13/005—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass by contact with at least one rotating roll
Abstract
A biodegradable brush wire comprises the following components in percentage by weight: 65 to 94 percent of polylactic acid; 2% -28% of flexible polyester; 3 to 8 percent of compatibilizer; 0.3 to 1.5 percent of nano particles; 0.2 to 1 percent of antioxidant; the flexible polyester is at least one of PBS, PBAT, PBST and PCL. The biodegradable brush wire has the advantages of good toughness, high strength, good heat resistance and higher elongation at break. A method for preparing the biodegradable brush filaments comprises the following steps: uniformly mixing polylactic acid, flexible polyester, a compatibilizer, nano particles and an antioxidant, performing melt extrusion at the temperature of 165-240 ℃, and performing devolatilization treatment to obtain primary raw silk; secondly, carrying out water bath cooling treatment and drafting treatment on the primary raw silk in the first step to obtain silk bundles; thirdly, the bundle of middle filaments is subjected to heat setting treatment, rolling treatment and drying treatment to obtain the brush filaments with the diameter of 0.08-0.35 mm. The preparation method of the biodegradable brush wire can remove unreacted residual micromolecules in the preparation process of the brush wire, and the safety of the brush wire is higher.
Description
Technical Field
The invention relates to the technical field of toothbrush filaments, in particular to a biodegradable toothbrush filament and a preparation method thereof.
Background
The toothbrush is an indispensable daily consumption article for human life, and the use amount is extremely large. At present, most of the common toothbrush filaments of people are made of polymer materials such AS nylon (PA), polybutylene terephthalate (PBT), polypropylene (PP) and the like, and the toothbrush handle is also made of polymer materials such AS acrylonitrile/styrene copolymer (AS), Polystyrene (PS), polyphenylene (PP), Thermoplastic Polyurethane (TPU) and the like. The materials are all non-degradable materials, can exist in the nature for hundreds of thousands of years, and are convenient for the life of people and also cause great pollution to the nature.
With the higher requirement of environmental protection, the biodegradable materials gradually enter the daily life of people. The biodegradable material can be subjected to a series of physical and chemical changes in compost and natural normal environment to finally change into carbon dioxide and water, and is finally nontoxic and harmless to the nature. The biodegradable materials which are produced in large scale at present comprise poly (butylene succinate) (PBS), polylactic acid (PLA), poly (butylene adipate terephthalate) (PBAT), poly (butylene succinate terephthalate) (PBST), poly (hydroxy fatty acid ester) (PHA) and the like.
Polylactic acid (PLA) is a completely biodegradable polymer material, has good biocompatibility and degradability, is nontoxic and harmless to human bodies, can be decomposed into carbon dioxide and water in a natural environment, has good strength, thermoplasticity, processability, transparency and the like, is suitable for various processing methods, is an ideal substitute material for petroleum-based plastics, and has antibacterial property, so that the PLA material has natural advantages as a brush wire raw material, particularly a toothbrush wire raw material. However, PLA has disadvantages of high brittleness, poor heat resistance, low elongation at break, and poor toughness, and thus its application in the field of general-purpose plastics is still limited.
In order to improve the toughness and heat resistance of PLA, researchers have adopted many methods including chemical methods such as copolymerization methods, physical methods such as blending methods to modify it. The chemical copolymerization method has complex process and high cost, and the physical blending is a relatively simple and easy method compared with the chemical copolymerization method, so the method has wider application. For example, chinese patent No. ZL03149911.2 (No. CN1475530A) discloses a biodegradable resin composition, which can improve the heat resistance of polylactic acid by adding inorganic fillers such as talc powder and montmorillonite, but the mechanical properties such as toughness are greatly reduced. For example, chinese patent No. ZL03117482.5 (No. CN1532216A) discloses a polylactic acid composition film, wherein polylactic acid is toughened and modified by small molecules such as citric acid ester, and the elongation at break of the obtained film is up to 330%, but the small molecules are easy to migrate to reduce the strength of the material, thereby limiting the application of polylactic acid.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide a biodegradable brush wire with good toughness, high strength, good heat resistance and high elongation at break.
The second technical problem to be solved by the present invention is to provide a method for preparing the biodegradable brush wire, which can remove residual molecules in the preparation process of the biodegradable brush wire, so that the safety of the biodegradable brush wire is higher, and the quality of the brush wire product is improved.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the biodegradable brush wire is characterized by comprising the following components in percentage by weight:
the flexible polyester is at least one of polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST) and Polycaprolactone (PCL).
The polylactic acid is a homopolymer or a copolymer of L-lactic acid and D-lactic acid, and the weight average molecular weight of the polylactic acid is 8-20 ten thousand.
Further contemplated, the compatibilizer is at least one of an aliphatic diisocyanate (HDI), an aromatic diisocyanate (MDI), and a cycloaliphatic diisocyanate (HTDI).
Further, the nano particles are at least one of titanium dioxide, calcium carbonate and aluminum oxide.
The antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076) and phenyl tris (2, 4-di-tert-butyl) phosphite. Wherein, the tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is an antioxidant 1010, the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester is an antioxidant 1076, and the tris (2, 4-di-tert-butyl) phenyl phosphite is an antioxidant 168.
The technical solution adopted by the present invention to solve the second technical problem is as follows: a method of preparing a biodegradable brush filament as defined above, comprising the steps of:
uniformly mixing polylactic acid, flexible polyester, a compatibilizer, nano particles and an antioxidant, performing melt extrusion at the temperature of 165-240 ℃, and performing devolatilization treatment to obtain primary raw silk;
step two, carrying out water bath cooling treatment and drafting treatment on the primary yarn obtained in the step one to obtain a tow;
and step three, carrying out heat setting treatment, winding treatment and drying treatment on the filament bundles obtained in the step two to obtain the brush filaments with the diameters of 0.08-0.35 mm.
More preferably, the polylactic acid and the flexible polyester are subjected to a pre-drying treatment before being mixed.
The water temperature of the water bath cooling treatment is 23-27 ℃.
The rolling treatment adopts the rolling of the rolling frame of square, and the rolling number of turns is 120 ~ 150 circles at every turn.
The drying temperature is 65-105 ℃, and the drying time is 0.5-4 h.
Further design, in the first step, a single-screw extruder is adopted to melt and extrude the mixed raw materials, a charging barrel of the single-screw extruder is provided with 6 heating sections from an inlet to an outlet, and the heating temperatures of the 6 heating sections are 165-175 ℃, 190-210 ℃, 195-215 ℃, 200-220 ℃, 220-240 ℃ and 210-230 ℃ in sequence.
In order to enable the devolatilization treatment effect to be better, the charging barrel of the single-screw extruder is provided with an exhaust hole between the fourth heating section and the fifth heating section, the diameter of the exhaust hole is 10-20 mm, and the devolatilization treatment is performed by a vacuum air extraction device connected with the exhaust hole.
In order to increase the strength of the degradable brush filaments, in the second step, the drafting device is provided with a first drafting roller, a second drafting roller and a third drafting roller, and the rotation speed ratio of the first drafting roller, the second drafting roller and the third drafting roller is 1: 3-5: 3.5 to 5.5. The fragility of the biodegradable brush filaments made of pure polylactic acid is large, so that the primary filaments made of pure polylactic acid can only bear about 3 times of drafting multiplying power, the breaking elongation of the degradable brush filaments can be improved by blending of flexible polyester and polylactic acid, the toughness of the blending material can bear large drafting multiplying power (about 3.5-5.5 times) is increased, the strength of the brush filaments can be effectively improved by the drafting of the primary filaments, and the strength of the primary filaments can be obviously improved by the large drafting multiplying power.
In order to improve the heat setting effect of the brush filaments, in the third step, the heat setting treatment is carried out by adopting a setting machine with double setting rollers, the temperature of the heat setting treatment is 100-135 ℃, the winding number of the filament bundles on the double setting rollers is 50-120, and the winding length of the filament bundles on the double setting rollers is 290-450 m.
Compared with the prior art, the invention has the advantages that: the biodegradable brush wire is characterized in that the flexible polyester with higher impact strength and elongation at break is added into polylactic acid to improve the toughness of a blending material, the compatibilizer has better reaction activity and can form a molecular bridge between the polylactic acid and the flexible polyester to improve the compatibility of the polylactic acid and the flexible polyester and enable the polylactic acid and the flexible polyester to be combined more stably, so that the mechanical property and stability of a blending system of the polylactic acid and the flexible polyester are improved, the addition of nano particles plays a role in enhancing toughening and crystallization nucleating agent on the blending system by utilizing the small-size effect and the surface effect of the nano particles to further improve the strength, the rigidity and the heat resistance of the modified blending material, and the addition of an antioxidant can reduce or avoid thermal degradation in the blending modification process of the polylactic acid and the flexible polyester as much as possible and plays a thermal stabilization role, so that the biodegradable brush wire has good toughness and heat resistance, The high strength and elongation at break can meet the requirements on fatigue resistance and rebound resilience of the toothbrush wire; the manufacturing method of the biodegradable brush wire removes residual molecules such as a compatibilizer or other harmful molecules in the preparation process of the biodegradable brush wire through devolatilization treatment, so that the safety of the biodegradable brush wire is higher, and the quality of a brush wire product is improved.
Detailed Description
The following examples further describe the present invention in detail.
First, sample preparation
(1) Samples were prepared according to the weight percentages of the examples shown below.
Example 1: 100% of PLA;
example 2: 70% of PLA, 15% of PBS and 15% of PBAT;
example 3: PLA 65%, PBS 14%, PBAT 14%, MDI 5%, titanium dioxide 1%, antioxidant 10101%
Example 4: 80% of PLA, 7.5% of PBS, 7.5% of PBAT, 4% of MDI, 0.5% of titanium dioxide and 10100.5% of antioxidant;
example 5: 80% of PLA, 15% of PBST, 4% of HDI, 0.5% of calcium carbonate and 10760.5% of antioxidant;
example 6: 80% of PLA, 15% of PCL, 4% of HTDI, 0.5% of alumina and 1680.5% of antioxidant;
example 7: 94% of PLA, 1% of PBS, 1% of PBAT, 3% of MDI, 0.5% of titanium dioxide and 10100.5% of antioxidant;
in each of the above examples, polylactic acid was a copolymer of L-lactic acid and D-lactic acid (wherein the molar ratio of L to D was 3: 7), and had a weight average molecular weight of 15 ten thousand.
(2) The preparation method of the samples of the above embodiments comprises the following steps:
uniformly mixing pre-dried polylactic acid, pre-dried flexible polyester, a compatibilizer, nano particles and an antioxidant, performing melt extrusion by using a single-screw extruder, and performing devolatilization treatment to obtain primary raw silk;
step two, cooling the primary yarn obtained in the step one in a water bath at 25 ℃, and drafting to obtain a tow;
and step three, carrying out heat setting treatment, winding treatment and drying treatment on the filament bundles obtained in the step two to obtain the brush filaments with the diameter of 0.18 mm.
In the first step, the main structure of the single screw extruder in this embodiment may refer to the structure of the single screw extruder disclosed in the chinese utility model patent No. ZL201820221727.6 (publication No. CN207842026), and the difference between the structure of the single screw extruder in this embodiment and the structure of the single screw extruder disclosed in this patent lies in: the charging barrel of the single screw extruder in the embodiment is provided with 6 heating sections from the inlet to the outlet, and the heating temperatures of the 6 heating sections are 170 ℃, 195 ℃, 200 ℃, 210 ℃, 230 ℃ and 220 ℃ in sequence; the vent hole is arranged between the fourth heating section and the fifth heating section, the diameter of the vent hole is 15mm, a vacuum pumping device is connected to the vent hole to perform devolatilization treatment on the mixed raw material in the melt extrusion process, and the vacuum pumping pressure of the vacuum pumping device is-0.1 MPa.
In the second step, the drafting treatment is carried out by adopting a drafting device with a first drafting roller, a second drafting roller and a third drafting roller, and the rotating speeds of the first drafting roller, the second drafting roller and the third drafting roller are 26.5 circles/min, 130 circles/min and 133 circles/min in sequence.
In the third step, the heat setting treatment adopts a setting machine with double setting rollers to carry out on-line setting, the structure of the setting machine can refer to the prior art and is not repeated herein, the temperature of the heat setting treatment is 130 ℃, the winding number of the filament bundles on the double setting rollers is 110 circles, and the winding length of the filament bundles on the double setting rollers is 300 m; the winding treatment adopts a square winding frame for winding, and the number of winding turns is 145 turns each time; the temperature of the drying treatment is 80 ℃, and the time is 3 h.
Second, sample performance testing
The samples of each example were subjected to a heat resistance temperature test, a bending recovery test, a tensile strength test and an elongation at break test, respectively. The heat-resisting temperature test method comprises the following steps: preparing brush wire segments with the length of 30 +/-0.2 mm, sequentially immersing the brush wire segments in hot water with the water temperature of 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃ for 3min, taking out the brush wire segments, absorbing water by using absorbent paper, observing whether the brush wire segments are bent or shrunk and deformed, wherein the temperature just deformed of the brush wire segments is the heat-resistant temperature; 3 parallel samples were taken each time for the heat resistance temperature test. The bend recovery test was carried out according to the 5.5.5 clause of the GB19342-2013 toothbrush Standard. The tensile strength and elongation at break were measured according to the method of GB/T1040-2018 "determination of tensile Properties of plastics", wherein the tensile speed was set at 40 mm/min.
The test results are shown in the following table:
table 1 results of performance test of each example
As shown in Table 1, the brush filaments prepared from the pure polylactic acid of example 1 were too brittle to be formed into filaments, and the heat resistance temperature, tensile strength and elongation at break of the sample of example 1 were measured using undrawn, unfixed, virgin filaments.
As shown in Table 1, when comparing example 1 with example 2, the bending recovery and elongation at break of the biodegradable brush filaments in example 2 are increased, while the heat-resistant temperature and tensile strength are decreased, causing the difference in the above test results because: the toughness of the flexible polyester is superior to that of polylactic acid, but the strength of the flexible polyester is lower than that of the polylactic acid, so that the toughness and the elongation at break of the biodegradable brush wire prepared by blending the flexible polyester and the polylactic acid can be improved, and the tensile strength and the heat resistance of the biodegradable brush wire prepared by pure polylactic acid are reduced.
As shown in Table 1, when comparing example 2 with examples 3 to 7, the heat resistance temperature, the bending recovery rate, the tensile strength and the elongation at break of the biodegradable brush filaments of examples 3 to 7 are significantly better than those of the biodegradable brush filaments of example 2, and although the tensile strength of the biodegradable brush filaments of examples 3 to 7 cannot be recovered to the level of the pure polylactic acid of example 1, the tensile strength of the biodegradable brush filaments of examples 3 to 7 is maintained at a higher level than that of the biodegradable brush filaments of example 2; the differences of the above test results are particularly shown in that the biodegradable brush filaments in examples 3 to 7 are not easily bent in hot water, are more easily recovered after bending, are not easily broken, and have better toughness; the reason for the above performance difference is that: the interface of the polylactic acid and the flexible polyester which are physically blended is incompatible, so that the interface of the polylactic acid and the flexible polyester is easy to layer in the drawing process of the brush wire to form brittle points, and further the biodegradable brush wire is broken, and the addition of the compatibilizer enables a molecular bridge to be formed between the polylactic acid and the flexible polyester so as to improve the compatibility of the polylactic acid and the flexible polyester, so that the polylactic acid and the flexible polyester are combined more stably, and the heat resistance, the toughness, the tensile strength and the elongation at break of the polylactic acid and flexible polyester blending system are improved jointly under the synergistic effect of the nanoparticles, the antioxidant and the compatibilizer.
As shown in table 1, when comparing examples 3, 4 and 7, the heat resistance temperature, the bending recovery rate and the elongation at break of the biodegradable brush filament are increased and then decreased with the decrease of the contents of the flexible polyester and the compatibilizer in the blending system, and the tensile strength is increased gradually and slightly, which indicates that the heat resistance, the toughness and the elongation at break of the biodegradable brush filament prepared by the blending system can be improved higher and maintained at a higher level only when the component ratio of the polylactic acid, the flexible polyester and the compatibilizer is proper, and the molecular bridge formed between the polylactic acid and the flexible polyester by the compatibilizer is reflected from the side, and the degree of the chemical bonding of the compatibilizer in the blending system greatly determines the improvement of the heat resistance, the toughness and the elongation at break of the biodegradable brush filament and the maintenance of the strength.
Claims (10)
1. The biodegradable brush wire is characterized by comprising the following components in percentage by weight:
the flexible polyester is at least one of polybutylene succinate, polybutylene adipate terephthalate, polybutylene succinate terephthalate and polycaprolactone.
2. The biodegradable brush wire according to claim 1, wherein said polylactic acid is a homopolymer or copolymer of L-lactic acid and D-lactic acid, and the weight average molecular weight of said polylactic acid is 8 to 20 ten thousand.
3. The biodegradable brush filament according to claim 1, wherein said compatibilizer is at least one of aliphatic diisocyanate, aromatic diisocyanate and alicyclic diisocyanate.
4. The biodegradable brush wire of claim 1, wherein said nanoparticles are at least one of titanium dioxide, calcium carbonate and aluminum oxide.
5. The biodegradable brush filament according to claim 1, wherein said antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and phenyl tris (2, 4-di-tert-butyl) phosphite.
6. A method for preparing biodegradable brush filaments according to any one of claims 1 to 5, comprising the steps of:
uniformly mixing polylactic acid, flexible polyester, a compatibilizer, nano particles and an antioxidant, performing melt extrusion at the temperature of 165-240 ℃, and performing devolatilization treatment to obtain primary raw silk;
step two, carrying out water bath cooling treatment and drafting treatment on the primary yarn obtained in the step one to obtain a tow;
and step three, carrying out heat setting treatment, winding treatment and drying treatment on the filament bundles obtained in the step two to obtain the brush filaments with the diameters of 0.08-0.35 mm.
7. The method for preparing biodegradable brush filaments according to claim 6, wherein in the first step, the mixed raw materials are melt-extruded by using a single screw extruder, a charging barrel of the single screw extruder is provided with 6 heating sections from an inlet to an outlet, and the heating temperature of the 6 heating sections is 165-175 ℃, 190-210 ℃, 195-215 ℃, 200-220 ℃, 220-240 ℃ and 210-230 ℃ in sequence.
8. The method for preparing biodegradable brush filaments according to claim 7, wherein a vent hole is formed between the fourth heating section and the fifth heating section on the barrel of the single-screw extruder, the diameter of the vent hole is 10-20 mm, and the devolatilization is performed by using a vacuum pumping device connected with the vent hole.
9. The method for preparing biodegradable brush filaments according to claim 6, wherein in the second step, the drawing process is performed by using a drawing device having a first drawing roller, a second drawing roller and a third drawing roller, and the rotation speed ratio of the first drawing roller, the second drawing roller and the third drawing roller is 1: 3-5: 3.5 to 5.5.
10. The method for preparing biodegradable brush filaments according to claim 6, wherein the heat-setting treatment is performed by a setting machine having a double setting roller in the third step, and the heat-setting treatment temperature is 100-135 ℃, the number of winding turns of the filament bundle on the double setting roller is 50-120, and the winding length of the filament bundle on the double setting roller is 290-450 m.
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