CN112813530A - Hydrophilic soft polylactic acid spinning composite material and preparation method thereof - Google Patents
Hydrophilic soft polylactic acid spinning composite material and preparation method thereof Download PDFInfo
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- CN112813530A CN112813530A CN202110100885.2A CN202110100885A CN112813530A CN 112813530 A CN112813530 A CN 112813530A CN 202110100885 A CN202110100885 A CN 202110100885A CN 112813530 A CN112813530 A CN 112813530A
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- polylactic acid
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- composite material
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 103
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000009987 spinning Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002667 nucleating agent Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000001408 amides Chemical class 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 21
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000003086 colorant Substances 0.000 claims abstract description 20
- 239000004902 Softening Agent Substances 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 11
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 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 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005453 pelletization Methods 0.000 claims description 4
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 3
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 3
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical compound N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 3
- 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 3
- 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 claims description 3
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- DJWFNQUDPJTSAD-UHFFFAOYSA-N n-octadecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC DJWFNQUDPJTSAD-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 3
- 239000004299 sodium benzoate Substances 0.000 claims description 3
- 235000010234 sodium benzoate Nutrition 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- YDQUROLTIDVHRK-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;propane-1,2,3-triol Chemical group OCC(O)CO.OC(=O)CC(O)(C(O)=O)CC(O)=O YDQUROLTIDVHRK-UHFFFAOYSA-N 0.000 claims 1
- WKZFQFQFYZJKPR-UHFFFAOYSA-N butanedioic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)CCC(O)=O WKZFQFQFYZJKPR-UHFFFAOYSA-N 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000013341 scale-up Methods 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- DQHHKFVACXSZHQ-UHFFFAOYSA-N 4-(2,3-dihydroxypropoxy)-4-oxobutanoic acid Chemical compound OCC(O)COC(=O)CCC(O)=O DQHHKFVACXSZHQ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VQENOYXMFIFHCY-UHFFFAOYSA-N Monoglyceride citrate Chemical group OCC(O)COC(=O)CC(O)(C(O)=O)CC(O)=O VQENOYXMFIFHCY-UHFFFAOYSA-N 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- VVLUUGNZSQRYFP-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid;terephthalic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 VVLUUGNZSQRYFP-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229940075529 glyceryl stearate Drugs 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004804 winding 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
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A hydrophilic soft polylactic acid spinning composite material and a preparation method thereof belong to the technical field of biodegradable spinning materials and preparation thereof. The method comprises the following steps: taking 71.7-92.8% of polylactic acid, 1-5% of polyester softening hydrophilic agent, 5-15% of degradable toughening agent, 0.5-5% of amide softening agent, 0.1-0.3% of nucleating agent, 0.1-1% of antioxidant and 0.5-2% of coloring agent as raw materials, and drying the polylactic acid; introducing the obtained raw materials into a high-speed mixer for mixing; and putting the obtained mixture into a double-screw extruder, performing melt extrusion under the conditions of controlling the rotating speed and the extrusion temperature of the screw, and cooling and granulating to obtain a finished product. The hydrophilic soft polylactic acid spinning composite material is ensured to have good spinnability, softness, hydrophilicity and degradability; various compatibilizers are not required to be added for modification; the process is simple, and the requirement of industrial scale-up production cannot be met.
Description
Technical Field
The invention belongs to the technical field of biodegradable spinning materials and preparation thereof, and particularly relates to a hydrophilic soft polylactic acid spinning composite material and a preparation method thereof.
Background
Plastic products made of petrochemical materials are widely applied in daily life of people, but the degree of environmental pollution is also increased correspondingly with the increase of the consumption of plastic packages, lunch boxes, express packages, cups, straws and the like, for example, marine environmental pollution becomes a global public hazard.
In order to protect the environment where human beings rely on to live, biodegradable plastics such as polylactic acid derived from biological raw materials are gaining favor because the biodegradable plastics have properties close to those of common plastics, but can be degraded into water and carbon dioxide again in natural soil environment, water environment or composting environment, i.e. in a stacked state after being discarded, can return to the natural environment without generating secondary pollution, and can be used as degradable plastic bags, disposable tableware, disposable plastic supplies for hotels and restaurants and express plastic packages in logistics industry in large scale.
As is known in the art, polylactic acid-based materials can be used as biodegradable biological fiber materials, and the biodegradable effect can be achieved when polylactic acid fibers (i.e., polylactic acid filaments) spun from the polylactic acid-based materials are used for manufacturing clothing fabrics and other products, such as bedding fabrics, and the like, after the polylactic acid fibers are discarded. However, the polylactic acid material has high rigidity and bending modulus of 3500MPa, so that the polylactic acid material can show stiff fabric hand feeling (namely poor hand feeling) and lack of skin-friendly effect when being used as a fabric fiber material; meanwhile, the elongation at break of the polylactic acid fiber is low, so that the ductility can not meet the requirements of people. Therefore, it is of positive significance to seek to solve the aforementioned technical problems of polylactic acid.
CN110444639A recommends "a soft and hydrolysis-resistant polylactic acid fiber and a preparation method thereof", the formula is (by weight portion): 200 parts of polylactic acid with molecular weight of 870000-890000-180, 7-10 parts of polyethylene glycol with molecular weight of 700, 0.1-1.2 parts of compatibilizer MDI and 0.1-2 parts of polycarbodiimide. CN102046861B discloses "polylactic acid fiber" and CN103069059A discloses "toughened polylactic acid fiber", both of which adopt similar methods to toughen and modify polylactic acid, and the composition comprises at least one polylactic acid with a content of 55-97 wt%, at least one plasticizer with a content of 2-25 wt% and at least one compatibilizer with a content of 1-20 wt%. CN105556014A discloses "polylactic acid mixed nonwoven fabric with improved flexibility and manufacturing method thereof" and CN102817179A discloses "a compostable and degradable surface layer material containing polylactic acid fiber cotton fiber and manufacturing method thereof", both of which patents adopt erucamide as a softening agent, but the system uses polyethylene polyolefin system, because polyolefin can not be completely degraded, the composition can not be regarded as the category of completely biodegradable material. In particular, the aforementioned patents require the compatibilization of polylactic acid and polyethylene glycol by using compatibilizers such as MDI (diphenylmethane diisocyanate) and maleic anhydride grafted polypropylene, but these compatibilizers have disadvantages such as toxicity of MDI (diphenylmethane diisocyanate) itself, and maleic anhydride grafted polypropylene is not a degradable material range and has residual macromolecules after the material is degraded. In any case, without being limited to the above cited patent documents, no suggestion is given that this would help to solve the above mentioned technical problems of polylactic acid, which the applicant has made in the following description.
Disclosure of Invention
The invention aims to provide a hydrophilic soft polylactic acid spinning composite material which is beneficial to embodying good spinnability, embodying ideal softness and hydrophilicity and embodying excellent degradability.
The invention also aims to provide a preparation method of the hydrophilic soft polylactic acid spinning composite material, and the method can ensure that the technical effect of the obtained hydrophilic soft polylactic acid spinning composite material can be comprehensively reflected.
The invention aims to provide a hydrophilic soft polylactic acid spinning composite material, which comprises the following raw materials in percentage by mass: 71.7 to 92.8 percent of polylactic acid, 1 to 5 percent of polyester softening hydrophilic agent, 5 to 15 percent of degradable toughening agent, 0.5 to 5 percent of amide softening agent, 0.1 to 0.3 percent of nucleating agent, 0.1 to 1 percent of antioxidant and 0.5 to 2 percent of coloring agent.
A hydrophilic soft polylactic acid spinning composite material comprises the following raw materials in percentage by mass: 71.7% of polylactic acid, 5% of polyester softening hydrophilic agent, 15% of degradable toughening agent, 5% of amide softening agent, 0.3% of nucleating agent, 1% of antioxidant and 2% of colorant.
A hydrophilic soft polylactic acid spinning composite material comprises the following raw materials in percentage by mass: 92.3 percent of polylactic acid, 1 percent of polyester softening hydrophilic agent, 5 percent of degradable toughening agent, 0.5 percent of amide softening agent, 0.2 percent of nucleating agent, 0.5 percent of antioxidant and 0.5 percent of colorant.
A hydrophilic soft polylactic acid spinning composite material comprises the following raw materials in percentage by mass: 83% of polylactic acid, 3% of polyester softening hydrophilic agent, 9.8% of degradable toughening agent, 3% of amide softening agent, 0.1% of nucleating agent, 0.1% of antioxidant and 1% of colorant.
In a specific embodiment of the present invention, the polylactic acid is a L-lactide type polylactic acid (PLLA) having a melt index of 20-30g/10min, a purity of 98% or more and a melting point of 160 ℃ or more.
In another specific embodiment of the present invention, the polyester softening hydrophilic agent is glyceryl citrate, glyceryl stearate, glyceryl succinate, diglyceride, triglyceride, alpha-glyceride, or beta-glyceride.
In yet another specific embodiment of the present invention, the degradable toughening agent is polybutylene terephthalate-adipate-butylene terephthalate (PBAT) with a melt index of 2-5g/10min and a melting point of 110-120 ℃ and/or polybutylene adipate-butylene terephthalate (PBS) with a melt index of 4-20g/10min and a melting point of 110-120 ℃; the amide softener is one or a combination of more of erucamide, oleamide, ethylene bis stearamide, octadecyl stearamide and octadecyl erucamide; the nucleating agent is one or a composition of more of superfine talcum powder with the diameter of less than 2 mu m, sodium benzoate nucleating agent, sorbitol nucleating agent, organic sodium phosphate and special nucleating agent potassium benzene sulfonate LAK-301 for polylactic acid; the antioxidant is one or a combination of more of an antioxidant 1010, an antioxidant 1076, an antioxidant 168, hydroxybenzophenone, hydroxybenzotriazole and a metal ion passivator; the colorant is titanium dioxide, carbon black or carbon black master batch.
The invention also aims to complete the task, and the preparation method of the hydrophilic soft polylactic acid spinning composite material comprises the following steps:
A) preparing materials, namely taking the following raw materials in percentage by mass: 71.7-92.8% of polylactic acid, 1-5% of polyester softening hydrophilic agent, 5-15% of degradable toughening agent, 0.5-5% of amide softening agent, 0.1-0.3% of nucleating agent, 0.1-1% of antioxidant and 0.5-2% of coloring agent, and drying the polylactic acid to obtain a raw material;
B) mixing, namely introducing the raw materials obtained in the step A) into a high-speed mixer for mixing to obtain a mixture;
C) melt extrusion, namely putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 40-44: 1 and the screw diameter of 65-75mm, melt extruding under the conditions of controlling the rotation speed and the extrusion temperature of the screw, cooling and pelletizing to obtain the hydrophilic soft polylactic acid spinning composite material.
In another specific embodiment of the invention, the drying temperature for drying the polylactic acid in the step a) is 75-85 ℃, the drying time is 4-8h, and the water content of the dried polylactic acid is controlled below 500 ppm.
In yet another embodiment of the present invention, the mixing time in step B) is 1-5 min; in the step C), the screw rotation speed is controlled to be 180-600rpm, and the screw extrusion temperature is controlled to be 160-220 ℃.
The technical scheme provided by the invention has the technical effects that: the raw materials and the mass percentage of the polylactic acid, the polyester softening hydrophilic agent, the degradable toughening agent, the amide softening agent, the nucleating agent, the antioxidant and the colorant are reasonably selected, so that the hydrophilic soft polylactic acid spinning composite material can be ensured to have good spinnability, softness, hydrophilicity and degradability; because the formula does not contain polyethylene glycol substances, various compatibilizers are not required to be added for modification; the preparation method provided is simple in process and free of harsh process elements, so that the requirement of industrial scale-up production can be met, and the obtained hydrophilic soft polylactic acid spinning composite material can comprehensively embody the technical effects.
Detailed Description
Example 1:
A) preparing materials, namely taking the following raw materials in percentage by mass: 71.7% of polylactic acid, 5% of a polyester softening hydrophilic agent, 15% of a degradable toughening agent, 5% of an amide softening agent, 0.3% of a nucleating agent, 1% of an antioxidant and 2% of a coloring agent, and drying the polylactic acid at 75 ℃ for 8 hours to enable the water content of the polylactic acid to be less than 500ppm to obtain a raw material, wherein the polylactic acid in the step is L-lactide type polylactic acid (PLLA) with a melt index of 20g/10min, a purity of more than 98% and a melting point of more than 160 ℃, the L-lactide type polylactic acid is commonly called L-lactide polylactic acid (the same applies hereinafter), the polyester softening hydrophilic agent in the step is glyceryl citrate, and the degradable toughening agent in the step is poly terephthalic acid-adipate-butylene glycol (PBAT) with a melt index of 2-5g/10min and a melting point of 110-120 ℃ and the poly adipate with a melt index of 4-20g/10min and a melting point of 110-120 ℃ in the step A mixture of butylene glycol ester (PBS) and ethylene glycol distearate (PBS) in the same or different weight ratios, wherein the amide softener is a mixture of erucamide, oleamide and ethylene bis stearamide in the same or different weight ratios, the nucleating agent in this step is sorbitol nucleating agent, the antioxidant in this step is antioxidant 1010, and the colorant in this step is titanium dioxide;
B) mixing materials, namely introducing the raw materials obtained in the step A) into a high-speed mixer to mix for 5min to obtain a mixture;
C) and C, melt extrusion, namely putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 40: 1 and the screw diameter of 70mm, melt extrusion under the conditions that the rotating speed of the screw is controlled to be 600rpm and the extrusion temperature of the screw is controlled to be 160 ℃, cooling and granulating to obtain the hydrophilic soft polylactic acid spinning composite material.
Example 2:
A) preparing materials, namely taking the following raw materials in percentage by mass: 92.3% of polylactic acid, 1% of polyester softening hydrophilic agent, 5% of degradable toughening agent, 0.5% of amide softening agent, 0.2% of nucleating agent, 0.5% of antioxidant and 0.5% of coloring agent, and drying the polylactic acid at 85 ℃ for 4h to ensure that the water content of the polylactic acid is less than 500ppm to obtain the raw material, wherein the polylactic acid in the step is L-lactide type polylactic acid (PLLA) with the melt index of 30g/10min, the purity of more than 98% and the melting point of more than 160 ℃, the L-lactide type polylactic acid is commonly called L-lactide polylactic acid (the same below), the polyester softening hydrophilic agent in the step is glyceryl succinate, the degradable toughening agent in the step is poly terephthalic acid-adipate-butylene glycol (PBAT) with the melt index of 2-5g/10min and the melting point of 110-120 ℃, the amide softening agent in the embodiment is octadecyl stearamide, the nucleating agent in the step is a mixture of sodium benzoate nucleating agent, sodium organophosphate and superfine talcum powder with the diameter of less than 2 mu m which are mixed according to any weight ratio, the antioxidant in the step is a mixture of antioxidant 1076, antioxidant 168 and antioxidant 1010 which are mixed according to the same weight ratio, and the colorant in the step is titanium black;
B) mixing materials, namely introducing the raw materials obtained in the step A) into a high-speed mixer to mix for 1min to obtain a mixture;
C) and C, melt extrusion, namely putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 42: 1 and the screw diameter of 65mm, melt extrusion under the conditions that the rotating speed of the screw is controlled to be 180rpm and the extrusion temperature of the screw is controlled to be 200 ℃, cooling and pelletizing to obtain the hydrophilic soft polylactic acid spinning composite material.
Example 3:
A) preparing materials, namely taking the following raw materials in percentage by mass: 83% of polylactic acid, 3% of a polyester softening hydrophilic agent, 9.8% of a degradable toughening agent, 3% of an amide softening agent, 0.1% of a nucleating agent, 0.1% of an antioxidant and 1% of a coloring agent, and drying the polylactic acid at 80 ℃ for 6 hours to enable the water content of the polylactic acid to be less than 500ppm to obtain a raw material, wherein the polylactic acid in the step is L-lactide type polylactic acid (PLLA) with a melt index of 25g/10min, a purity of more than 98% and a melting point of more than 160 ℃, the L-lactide type polylactic acid is commonly called L-lactide polylactic acid (the same below), the polyester softening hydrophilic agent in the step is alpha-glyceride or glyceryl stearate, the degradable toughening agent in the step is poly adipic acid-butanediol ester (PBS) with a melt index of 4-20g/10min and a melting point of 110-120 ℃, the amide softening agent in the embodiment is oleamide, the nucleating agent in the step is potassium benzenesulfonate LAK-301 which is a special nucleating agent for polylactic acid, the antioxidant in the step is a mixture of hydroxybenzophenone and hydroxybenzotriazole which are mixed according to any weight ratio, and the coloring agent in the step is carbon black master batch;
B) mixing materials, namely introducing the raw materials obtained in the step A) into a high-speed mixer to mix for 3min to obtain a mixture;
C) and C, melt extrusion, namely putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 44: 1 and the screw diameter of 75mm, melt extrusion under the conditions that the rotating speed of the screw is controlled to be 350rpm and the extrusion temperature of the screw is controlled to be 190 ℃, cooling and pelletizing to obtain the hydrophilic soft polylactic acid spinning composite material.
When the hydrophilic soft polylactic acid spinning composite material obtained in the embodiments 1 to 3 is spun, the spinning temperature is 200-250 ℃, and the winding speed is 1000-1600 m/min; at the drawing station, the temperature of the hot plate is 100-150 ℃, and the drawing multiple is 2-6 times, and after drawing and rolling, the hydrophilic soft polylactic acid spinning composite fiber product can be obtained.
Comparative example 1:
the formulation of this comparative example consisted of:
the data obtained by comparing examples 1-3 with comparative example 1 are shown in the following table:
the evaluation method comprises the following steps:
drying the particles granulated by the double screws at the drying condition of 80 ℃ for 4-8 hours, then putting the particles into an injection molding machine, and performing injection molding by adopting an ISO 294 standard mold, wherein hydrophilicity is represented by surface resistance, the lower the surface resistance is, the better the hydrophilicity is, meanwhile, spinnability is obtained by observing the yarn breakage rate of 100 yarns, if the yarn breakage rate exceeds 5 yarns, the spinnability is not available, 2 or the following yarn breakage is good, 2-5 yarns are general, and other mechanical and thermal test standards are as follows:
| test items | Test method |
| Mechanical properties | |
| Tensile breaking strength | ISO 527-1/-2 |
| Elongation at tensile break | ISO 527-1/-2 |
| Bending strength | ISO 178 |
| Flexural modulus | ISO 178 |
| Notched izod impact strength 23 deg.c | ISO 180/1eA |
| Thermal performance | |
| Heat distortion temperature (0.45MPa) | ISO 75 |
| Others | |
| Surface resistance | IEC 60079 |
| Density of | ISO 1183 |
According to the test, the bending modulus, the surface resistance and whether the composite can be spun are low in several aspects, and in the composite added with the polyester softening hydrophilic agent such as glyceryl monostearate, the material has low surface resistance and hydrophilicity, and the bending modulus is lower, so that the fiber is softer, and meanwhile, as the composite does not contain polyethylene glycol substances, various compatibilizers are not required to be added for modification.
In a word, compared with the prior art, the invention has the advantages that the amide softener and the ester softener are combined, the rigidity of the material is further reduced by adding the polybutylene terephthalate-adipate-butanediol ester or the polybutylene adipate-butanediol ester toughening agent, and the spinnability and flexibility of the material are ensured.
Claims (10)
1. A hydrophilic soft polylactic acid spinning composite material is characterized by comprising the following raw materials in percentage by mass: 71.7 to 92.8 percent of polylactic acid, 1 to 5 percent of polyester softening hydrophilic agent, 5 to 15 percent of degradable toughening agent, 0.5 to 5 percent of amide softening agent, 0.1 to 0.3 percent of nucleating agent, 0.1 to 1 percent of antioxidant and 0.5 to 2 percent of coloring agent.
2. The hydrophilic soft polylactic acid spinning composite material as claimed in claim 1, is characterized by comprising the following raw materials in percentage by mass: 71.7% of polylactic acid, 5% of polyester softening hydrophilic agent, 15% of degradable toughening agent, 5% of amide softening agent, 0.3% of nucleating agent, 1% of antioxidant and 2% of colorant.
3. The hydrophilic soft polylactic acid spinning composite material as claimed in claim 1, is characterized by comprising the following raw materials in percentage by mass: 92.3 percent of polylactic acid, 1 percent of polyester softening hydrophilic agent, 5 percent of degradable toughening agent, 0.5 percent of amide softening agent, 0.2 percent of nucleating agent, 0.5 percent of antioxidant and 0.5 percent of colorant.
4. The hydrophilic soft polylactic acid spinning composite material as claimed in claim 1, is characterized by comprising the following raw materials in percentage by mass: 83% of polylactic acid, 3% of polyester softening hydrophilic agent, 9.8% of degradable toughening agent, 3% of amide softening agent, 0.1% of nucleating agent, 0.1% of antioxidant and 1% of colorant.
5. A hydrophilic flexible polylactic acid spun composite according to any of claims 1 to 4, characterized in that the polylactic acid is L-lactide type polylactic acid with a melt index of 20-30g/10min, a purity of above 98% and a melting point above 160 ℃.
6. A hydrophilic soft polylactic acid spun composite according to any of claims 1 to 4, characterized in that the polyester softening hydrophilic agent is glycerol citrate, glycerol stearate, glycerol succinate, diglyceride, triglyceride, alpha-glyceride or beta-glyceride.
7. The hydrophilic soft polylactic acid spinning composite material as claimed in any one of claims 1 to 4, wherein the degradable toughening agent is polybutylene terephthalate-adipate with a melt index of 2-5g/10min and a melting point of 110-120 ℃ and/or polybutylene adipate with a melt index of 4-20g/10min and a melting point of 110-120 ℃; the amide softener is one or a combination of more of erucamide, oleamide, ethylene bis stearamide, octadecyl stearamide and octadecyl erucamide; the nucleating agent is one or a composition of more of superfine talcum powder with the diameter of less than 2 mu m, sodium benzoate nucleating agent, sorbitol nucleating agent, organic sodium phosphate and special nucleating agent potassium benzene sulfonate LAK-301 for polylactic acid; the antioxidant is one or a combination of more of an antioxidant 1010, an antioxidant 1076, an antioxidant 168, hydroxybenzophenone, hydroxybenzotriazole and a metal ion passivator; the colorant is titanium dioxide, carbon black or carbon black master batch.
8. A method of making the hydrophilic soft polylactic acid spun composite of claim 1, comprising the steps of:
A) preparing materials, namely taking the following raw materials in percentage by mass: 71.7-92.8% of polylactic acid, 1-5% of polyester softening hydrophilic agent, 5-15% of degradable toughening agent, 0.5-5% of amide softening agent, 0.1-0.3% of nucleating agent, 0.1-1% of antioxidant and 0.5-2% of coloring agent, and drying the polylactic acid to obtain a raw material;
B) mixing, namely introducing the raw materials obtained in the step A) into a high-speed mixer for mixing to obtain a mixture;
C) melt extrusion, namely putting the mixture obtained in the step B) into a double-screw extruder with the length-diameter ratio of 40-44: 1 and the screw diameter of 65-75mm, melt extruding under the conditions of controlling the rotation speed and the extrusion temperature of the screw, cooling and pelletizing to obtain the hydrophilic soft polylactic acid spinning composite material.
9. The method for preparing the hydrophilic soft polylactic acid spinning composite material according to the claim 8, characterized in that the drying temperature for drying the polylactic acid in the step A) is 75-85 ℃, the drying time is 4-8h, and the water content of the dried polylactic acid is controlled below 500 ppm.
10. The method for preparing a hydrophilic soft polylactic acid spinning composite material according to claim 8, wherein the mixing time in the step B) is 1-5 min; in the step C), the screw rotation speed is controlled to be 180-600rpm, and the screw extrusion temperature is controlled to be 160-220 ℃.
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