CN115260719B - Preparation of efficient flame-retardant anti-dripping core-shell particles and polylactic acid material - Google Patents
Preparation of efficient flame-retardant anti-dripping core-shell particles and polylactic acid material Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 110
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002245 particle Substances 0.000 title claims abstract description 46
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 45
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 44
- 239000011258 core-shell material Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 claims abstract description 35
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 23
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940068041 phytic acid Drugs 0.000 claims abstract description 23
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 23
- 239000000467 phytic acid Substances 0.000 claims abstract description 23
- -1 siloxane chain Chemical group 0.000 claims abstract description 15
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 7
- 238000006243 chemical reaction Methods 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 239000010410 layer Substances 0.000 abstract description 12
- 239000012792 core layer Substances 0.000 abstract description 5
- 230000000295 complement effect Effects 0.000 abstract description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000915639 Homo sapiens Zinc finger protein 470 Proteins 0.000 description 1
- 102100029038 Zinc finger protein 470 Human genes 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses preparation of high-efficiency flame-retardant anti-dripping core-shell particles and a polylactic acid material, and relates to the technical field of functional modification of polylactic acid.A high-efficiency flame-retardant effect of DOPO and a high-efficiency anti-dripping effect of siloxane and a flame-retardant enhancement effect of phytic acid are utilized, so that the obtained flame-retardant anti-dripping core-shell particles have the high-efficiency flame-retardant anti-dripping effect, and excellent flame-retardant anti-dripping performance of a PLA material can be endowed with only a small addition amount; the phosphorus-silicon hybrid flame retardant is used as a core layer material, the soft core is obtained based on the flexibility of a siloxane chain segment, the rigid six-membered ring structure of the shell layer phytic acid is exactly complementary with the flexible core layer siloxane structure, and the core-shell particle with the soft core-shell structure is obtained, so that the flame retardant and anti-molten drop effect is achieved.
Description
Technical field:
the invention relates to the technical field of polylactic acid functional modification, in particular to preparation of high-efficiency flame-retardant anti-dripping core-shell particles and a polylactic acid material.
The background technology is as follows:
polylactic acid (PLA) is an environment-friendly high polymer material, has good biocompatibility and degradability, and is considered as an environment-friendly bio-based material with wide development prospect. However, the elemental composition (carbon, hydrogen, oxygen) and molecular chain structure (ester bonds are easily broken at high temperatures to produce volatile combustibles) of PLA determine that it has the same disadvantages of being flammable as general polymers. And polylactic acid is used as a thermoplastic material, burns and is accompanied with serious molten drop phenomenon, and is easy to cause secondary fire to cause serious personal and property loss, so that the improvement of the flame-retardant molten drop resistance of the polylactic acid is significant in expanding the application range of the polylactic acid and improving the added value of a polylactic acid product.
In order to improve the flame retardant property of PLA, scientific researchers have developed a great deal of researches, such as adopting phosphorus-containing flame retardants such as ammonium polyphosphate, aluminum hypophosphite, phosphazene, DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and the like and a compound flame retardant system thereof or taking the phosphorus-containing flame retardants as an acid source to prepare an intumescent flame retardant system, synthesizing a novel phosphorus-nitrogen flame retardant, adopting a phosphorus-containing bio-based flame retardant, a nano flame retardant and the like. However, there are few solutions for flame retarding and anti-dripping of PLA in the prior art, and the addition of flame retardants to PLA materials by blending methods has a negative impact on the physical and mechanical properties of PLA.
The invention comprises the following steps:
the invention aims to solve the technical problem of providing a core-shell particle which has the functions of flame retardance and molten drop resistance and can toughen PLA, and the core-shell particle is applied to preparing flame retardance and molten drop resistance PLA materials.
According to the invention, DOPO is selected as a phosphorus-containing flame-retardant component, vinyl siloxane is an unsaturated silicon-containing precursor, the vinyl siloxane reacts with DOPO to obtain a phosphorus-containing silicon hybrid flame retardant, the phosphorus-containing silicon hybrid flame retardant is used as a nuclear layer material, and good flame-retardant and anti-dripping effects are obtained by utilizing the efficient flame-retardant effect of DOPO and the efficient anti-dripping effect of siloxane; the shell material is phytic acid which is rich in phosphorus element, is an environment-friendly biomass flame retardant, can further enhance the flame retardant effect, has a rigid six-membered ring structure and is exactly complementary with a flexible core-layer siloxane structure, so that the core-shell particles with a soft core-shell structure are obtained, and have the toughening effect while being flame retardant and anti-molten drop.
The first object of the invention is to provide a preparation method of flame-retardant anti-dripping core-shell particles, which comprises the following steps:
(1) Adding a solvent, DOPO and vinyl siloxane into a reaction kettle, introducing nitrogen for protection, heating and stirring after the nitrogen is saturated until the DOPO is completely dissolved;
(2) Dissolving an initiator in a solvent in advance, then slowly dropwise adding the initiator into the mixed solution of DOPO and vinyl silane, heating to react, cooling to room temperature after the reaction is finished, and removing the solvent and unreacted vinyl siloxane to obtain the phosphorus-silicon hybrid monomer flame retardant;
(3) Sequentially dropwise adding ethanol and water into the prepared phosphorus-silicon hybrid monomer flame retardant while stirring, adjusting the pH value of the solution by adopting a pH regulator after the dropwise adding is completed, and heating to react to obtain the phosphorus-silicon hybrid polymer flame retardant;
(4) Adding phytic acid into water, regulating the pH value of the solution by adopting a pH regulator, and stirring for dissolution; and then dripping phytic acid water solution into the phosphorus-silicon hybrid polymeric flame retardant, heating to react, and filtering, washing and drying after the reaction is finished to obtain the flame-retardant anti-dripping core-shell particles.
In the step (1), the vinyl siloxane is vinyl trimethoxy silane or vinyl triethoxy silane; the solvent is chloroform, isopropanol or ethyl acetate, the dosage is 2/3-4/5 of the total dosage of the solvent, and the mass ratio of DOPO to the solvent is 1:8-1:4; the molar ratio of DOPO to vinylsilane is 1:1-1:1.3.
In the step (2), the initiator is azodiisobutyronitrile, and the dosage is 0.5-1% of DOPO mass; the solvent is chloroform, isopropanol or ethyl acetate, and the dosage is 1/5-1/3 of the total dosage of the solvent; the temperature of the heating reaction is 60-80 ℃ and the time is 8-12 h.
In the step (3), the mol ratio of the phosphorus-silicon hybrid monomer flame retardant to the ethanol to the water is 1:2:20-1:5:30; the pH regulator is Na 2 CO 3 Aqueous solutions or ammonia; the pH value of the solution is 8-10; the temperature of the heating reaction is 40-60 ℃ and the time is 2-4 h.
In the step (4), the pH regulator is Na 2 CO 3 Aqueous solutions or ammonia; the pH value of the solution is 8-10; the mass ratio of the phytic acid to the water is 1:5-1:10; the mass ratio of the phytic acid to the phosphorus-silicon hybrid polymeric flame retardant is 2:3-3:2; the temperature of the heating reaction is 40-60 ℃ and the time is 2-4 h.
The second object of the invention is to provide a flame-retardant anti-dripping core-shell particle prepared by the preparation method.
The third object of the invention is to provide a flame-retardant anti-dripping polylactic acid material, which comprises the flame-retardant anti-dripping core-shell particles. Namely, the flame-retardant anti-dripping core-shell particles are adopted as the flame retardant.
The preparation method of the flame-retardant anti-dripping polylactic acid material comprises the steps of uniformly mixing PLA and flame-retardant anti-dripping core-shell particles, adding the mixture into a double-screw extruder for extrusion granulation, and performing hot-pressing treatment to obtain the required shape.
The mass ratio of the flame-retardant anti-dripping core-shell particles to PLA is 1-10%, preferably 2-5%; the melting temperature is 170-190 ℃ and the rotating speed is 200-250rpm.
The beneficial effects of the invention are as follows:
1. the invention utilizes the efficient flame retardant effect of DOPO and the efficient molten drop inhibition effect of siloxane, so that the prepared phosphorus-silicon hybrid flame retardant has excellent flame retardant and molten drop resistant effects; the phytic acid is rich in phosphorus, is an environment-friendly biomass flame retardant, and can further enhance the flame retardant effect. The obtained flame-retardant anti-dripping core-shell particles have high-efficiency flame-retardant anti-dripping effect, and can endow PLA materials with excellent flame-retardant anti-dripping performance only by small addition amount.
2. According to the invention, the phosphorus-silicon hybrid flame retardant is used as a core layer material, and a soft core is obtained based on the flexibility of a siloxane chain segment; the shell phytic acid is of a rigid six-membered ring structure and is exactly complementary with a flexible core-layer siloxane structure, so that the core-shell particles with a soft core-hard shell structure are obtained, and the flame-retardant and anti-dripping core-shell particle has a toughening effect.
The specific embodiment is as follows:
the invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
Example 1
(1) 1L of chloroform, 216g of DOPO and 148g of vinyltrimethoxysilane are added into a four-port reaction kettle provided with a stirrer, a constant pressure dropping funnel, a thermometer and a condenser, nitrogen is introduced for protection, the temperature is raised to 60 ℃ after the nitrogen is saturated, and the stirring is continued until the DOPO is completely dissolved.
(2) 12g of azobisisobutyronitrile is dissolved in 500mL of chloroform in advance, and then the azobisisobutyronitrile solution is slowly dripped into the DOPO and vinyl trimethoxysilane solution, and the dripping is completed within 2 hours, and the reaction is carried out at 60 ℃ for 12 hours. After the reaction is finished, cooling to room temperature, and removing the solvent chloroform by rotary evaporation to obtain the phosphorus-silicon hybrid monomer flame retardant.
(3) The prepared phosphorus-silicon hybrid monomer flame retardant is stirred sequentiallyDripping 100g of ethanol and 360g of water, and after the dripping is finished, using Na 2 CO 3 And regulating the pH value of the system to 8 by using the aqueous solution, increasing the temperature to 60 ℃, and carrying out heat preservation reaction for 4 hours to obtain the nuclear layer phosphorus-silicon hybrid polymeric flame retardant.
(4) 240g of phytic acid was added to 1.2L of water using Na 2 CO 3 The pH value of the aqueous solution is adjusted to 8, and the aqueous solution is stirred and dissolved. And (3) dripping the phytic acid aqueous solution into the nuclear layer phosphorus-silicon hybrid polymeric flame retardant, uniformly stirring, heating to 60 ℃, preserving heat for reaction for 2 hours, filtering, washing and drying to obtain the flame-retardant anti-dripping nuclear shell particles.
(5) After 25g of flame-retardant anti-dripping core-shell particles and 2.5kg of PLA particles are uniformly mixed, the mixture is added into a double-screw extruder to be melt-blended at 190 ℃ at the rotating speed of 250rpm, extruded and granulated, and then the mixture is subjected to hot pressing treatment at 190 ℃ to obtain a strip-shaped material with the thickness of 2 mm.
Example 2
(1) 1.5L of isopropanol, 216g of DOPO and 190g of vinyltrimethoxysilane are added into a four-port reaction kettle provided with a stirrer, a constant pressure dropping funnel, a thermometer and a condenser, nitrogen is introduced for protection, the temperature is raised to 80 ℃ after the nitrogen is saturated, and the stirring is continued until the DOPO is completely dissolved.
(2) 20g of azobisisobutyronitrile was dissolved in 500mL of isopropanol in advance, and then the azobisisobutyronitrile solution was slowly added dropwise to the DOPO and vinyltrimethoxysilane solution, and the reaction was carried out at 80℃for 8 hours after the dropwise addition was completed within 2 hours. And after the reaction is finished, cooling to room temperature, and removing the solvent isopropanol by rotary evaporation to obtain the phosphorus-silicon hybrid monomer flame retardant.
(3) Adding 230g of ethanol and 480g of water into the prepared phosphorus-silicon hybrid monomer flame retardant in sequence while stirring, and using Na after the addition 2 CO 3 And regulating the pH value of the system to 9 by using the aqueous solution, increasing the temperature to 50 ℃, and carrying out heat preservation reaction for 3 hours to obtain the nuclear layer phosphorus-silicon hybrid polymeric flame retardant.
(4) 400g of phytic acid was added to 2L of water using Na 2 CO 3 The pH value of the aqueous solution is adjusted to 9, and the aqueous solution is stirred and dissolved. Dripping phytic acid water solution into the nuclear layer phosphorus silicon hybridization polymerization flame retardant, uniformly stirring, heating to 40 ℃ for heat preservation reaction for 4 hours, filtering, washing and drying to obtain the flame retardant and anti-melting agentAnd (3) dripping core-shell particles.
(5) After 50g of flame-retardant anti-dripping core-shell particles and 2.5kg of PLA particles are uniformly mixed, the mixture is added into a double-screw extruder to be melt-blended at 170 ℃ and a rotating speed of 200rpm, extruded and granulated, and then the mixture is subjected to hot pressing treatment at 170 ℃ to obtain a strip-shaped material with the thickness of 2 mm.
Example 3
(1) 800mL of ethyl acetate, 108g of DOPO and 115g of vinyltriethoxysilane are added into a four-port reaction kettle provided with a stirrer, a constant-pressure dropping funnel, a thermometer and a condenser, nitrogen is introduced for protection, the temperature is raised to 70 ℃ after the nitrogen is saturated, and the stirring is continued until the DOPO is completely dissolved.
(2) 10g of azobisisobutyronitrile was dissolved in 400mL of ethyl acetate in advance, and then the azobisisobutyronitrile solution was slowly added dropwise to the DOPO and vinyltrimethoxysilane solution, and the dropwise addition was completed within 2 hours, and the reaction was carried out at 70℃for 10 hours. After the reaction is finished, the temperature is reduced to room temperature, and the solvent ethyl acetate is removed by rotary evaporation, so that the phosphorus-silicon hybrid monomer flame retardant is obtained.
(3) 70g of ethanol and 225g of water are sequentially added into the prepared phosphorus-silicon hybrid monomer flame retardant while stirring, and Na is used after the addition 2 CO 3 And regulating the pH value of the system to 10 by using the aqueous solution, increasing the temperature to 40 ℃, and carrying out heat preservation reaction for 4 hours to obtain the nuclear layer phosphorus-silicon hybrid polymeric flame retardant.
(4) 320g of phytic acid was added to 1.6L of water using Na 2 CO 3 The pH value of the aqueous solution is adjusted to 9, and the aqueous solution is stirred and dissolved. And (3) dripping the phytic acid aqueous solution into the nuclear layer phosphorus-silicon hybrid polymeric flame retardant, uniformly stirring, heating to 50 ℃ and preserving heat for reaction for 2 hours. Filtering, washing and drying to obtain the flame-retardant anti-dripping core-shell particles.
(5) After 75g of flame-retardant anti-dripping core-shell particles and 2.5kg of PLA particles are uniformly mixed, the mixture is added into a double-screw extruder to be melt-blended at 180 ℃ and a rotating speed of 250rpm, extruded and granulated, and then the mixture is subjected to hot pressing treatment at 180 ℃ to obtain a strip-shaped material with the thickness of 2 mm.
Example 4
(1) 600mL of isopropanol, 108g of DOPO and 95g of vinyltrimethoxysilane are added into a four-port reaction kettle provided with a stirrer, a constant pressure dropping funnel, a thermometer and a condenser, nitrogen is introduced for protection, the temperature is raised to 60 ℃ after the nitrogen is saturated, and the stirring is continued until the DOPO is completely dissolved.
(2) 6g of azobisisobutyronitrile is dissolved in 120mL of isopropanol in advance, and then the azobisisobutyronitrile solution is slowly dripped into the DOPO and vinyltrimethoxysilane solution, and the dripping is completed within 2 hours, and the reaction is carried out at 60 ℃ for 12 hours. And after the reaction is finished, cooling to room temperature, and removing the solvent isopropanol by rotary evaporation to obtain the phosphorus-silicon hybrid monomer flame retardant.
(3) And (3) sequentially dropwise adding 50g of ethanol and 270g of water into the prepared phosphorus-silicon hybrid monomer flame retardant while stirring, regulating the pH value of the system to 9 by using ammonia water after the dropwise adding is finished, raising the temperature to 50 ℃, and carrying out heat preservation reaction for 3 hours to obtain the nuclear layer phosphorus-silicon hybrid polymer flame retardant.
(4) 200g of phytic acid was added to 2L of water, the pH was adjusted to 9 with an aqueous ammonia solution, and the mixture was dissolved with stirring. And (3) dripping the phytic acid aqueous solution into the nuclear layer phosphorus-silicon hybrid polymeric flame retardant, uniformly stirring, heating to 50 ℃, and carrying out heat preservation reaction for 3 hours. Filtering, washing and drying to obtain the flame-retardant anti-dripping core-shell particles.
(5) 100g of flame-retardant anti-dripping core-shell particles and 2.5kg of PLA particles are uniformly mixed, then added into a double-screw extruder to be melt-blended at 190 ℃ at a rotating speed of 200rpm, extruded and granulated, and then subjected to hot pressing treatment at 190 ℃ to obtain a strip-shaped material with the thickness of 2 mm.
Example 5
(1) 1.2L of chloroform, 216g of DOPO and 170g of vinyl trimethoxy silane are added into a four-port reaction kettle provided with a stirrer, a constant pressure dropping funnel, a thermometer and a condenser, nitrogen is introduced for protection, the temperature is raised to 80 ℃ after the nitrogen is saturated, and the temperature is kept for continuous stirring until the DOPO is completely dissolved.
(2) 20g of azobisisobutyronitrile is dissolved in 800mL of chloroform in advance, and then the azobisisobutyronitrile solution is slowly dripped into the DOPO and vinyl trimethoxysilane solution, and the dripping is completed within 2 hours, and the reaction is carried out at 80 ℃ for 10 hours. After the reaction is finished, cooling to room temperature, and removing the solvent chloroform by rotary evaporation to obtain the phosphorus-silicon hybrid monomer flame retardant.
(3) The middle edge of the prepared phosphorus-silicon hybrid monomer flame retardantAdding 120g ethanol and 450g water dropwise under stirring, and adding Na 2 CO 3 And regulating the pH value of the system to 9 by using the aqueous solution, increasing the temperature to 50 ℃, and carrying out heat preservation reaction for 3 hours to obtain the nuclear layer phosphorus-silicon hybrid polymeric flame retardant.
(4) 260g of phytic acid was added to 1.5L of water using Na 2 CO 3 The pH value of the aqueous solution is adjusted to 9, and the aqueous solution is stirred and dissolved. And (3) dripping the phytic acid aqueous solution into the nuclear layer phosphorus-silicon hybrid polymeric flame retardant, uniformly stirring, heating to 40 ℃ and preserving heat for reaction for 4 hours. Filtering, washing and drying to obtain the flame-retardant anti-dripping core-shell particles.
(5) 125g of flame-retardant anti-dripping core-shell particles and 2.5kg of PLA particles are uniformly mixed, then the mixture is added into a double-screw extruder to be melt-blended at 190 ℃ at the rotating speed of 200rpm, extruded and granulated, and then the mixture is subjected to hot pressing treatment at 190 ℃ to obtain the strip-shaped material with the thickness of 2 mm.
Examples 6 to 10
Referring to example 5, the amounts of flame retardant anti-drip core-shell particles were replaced with 6% (example 6), 7% (example 7), 8% (example 8), 9% (example 9) and 10% (example 10), respectively, of the polylactic acid chips.
Comparative example 1
Directly melt-blending polylactic acid particles at 180 ℃ at a rotating speed of 200rpm, extruding and granulating, and performing hot pressing treatment at 190 ℃ to obtain a strip-shaped material with the thickness of 2 mm.
Performance test:
the tensile property of the material is tested by adopting an H5K-S type universal electronic testing machine according to the tensile strength test standard GB/T1040-2006.
The limiting oxygen index of the material is tested by adopting an FAA type oxygen index meter according to the oxygen index method test standard GB/T5454-1997 of combustion performance test.
Vertical burn Performance of materials test methods for measuring comparative burn performance of solid plastics in a vertical position according to ASTM D3801-2010, using a vertical burn tester model CZF-1.
Table 1 shows the flame retardant and anti-dripping properties and the physical and mechanical properties of the polylactic acid materials obtained in examples 1 to 10 and comparative example 1.
TABLE 1
As can be seen from Table 1, the flame retardant and anti-dripping core-shell particles prepared by the embodiment of the invention have high-efficiency flame retardant and anti-dripping effects. When the addition amount is only 2%, the molten drop phenomenon of PLA material can be obviously inhibited when the PLA material burns, and the vertical burning reaches V-1 level; when the addition amount is 5%, the PLA material burns without molten drops, the vertical burning reaches V-0 level, and the limiting oxygen index reaches 29.6%; if the flame retardant property of PLA needs to be further improved, the dosage of flame retardant anti-dripping core-shell particles can be increased. Because of the specially designed flame retardant structure, after the flame retardant anti-dripping core-shell particles are blended with PLA, the toughness of the PLA is improved. The above examples show that the core-shell particles prepared by the invention successfully endow PLA with excellent flame retardant and anti-dripping functions, and have a certain toughening effect due to the soft core-shell structure.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A preparation method of flame-retardant anti-dripping core-shell particles is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding a solvent, DOPO and vinyl siloxane into a reaction kettle, introducing nitrogen for protection, heating and stirring after the nitrogen is saturated until the DOPO is completely dissolved;
(2) Dissolving an initiator in a solvent in advance, then slowly dropwise adding the initiator into the mixed solution of DOPO and vinyl siloxane, heating to react, cooling to room temperature after the reaction is finished, and removing the solvent and unreacted vinyl siloxane to obtain the phosphorus-silicon hybrid monomer flame retardant;
(3) Sequentially dropwise adding ethanol and water into the prepared phosphorus-silicon hybrid monomer flame retardant while stirring, adjusting the pH value of the solution by adopting a pH regulator after the dropwise adding is completed, and heating to react to obtain the phosphorus-silicon hybrid polymer flame retardant;
(4) Adding phytic acid into water, regulating the pH value of the solution by adopting a pH regulator, and stirring for dissolution; then dripping phytic acid water solution into the phosphorus-silicon hybrid polymeric flame retardant, heating to react, filtering, washing and drying after the reaction is finished to obtain flame-retardant anti-dripping core-shell particles;
in the step (1), the vinyl siloxane is vinyl trimethoxy silane or vinyl triethoxy silane; the solvent is chloroform, isopropanol or ethyl acetate, the dosage is 2/3-4/5 of the total dosage of the solvent, and the mass ratio of DOPO to the solvent is 1:8-1:4; the molar ratio of DOPO to vinyl siloxane is 1:1-1:1.3;
in the step (2), the initiator is azodiisobutyronitrile, and the dosage is 0.5-1% of DOPO mass; the solvent is chloroform, isopropanol or ethyl acetate, and the dosage is 1/5-1/3 of the total dosage of the solvent; the temperature of the heating reaction is 60-80 ℃ and the time is 8-12 h;
in the step (3), the mol ratio of the phosphorus-silicon hybrid monomer flame retardant to the ethanol to the water is 1:2:20-1:5:30; the pH regulator is Na 2 CO 3 Aqueous solutions or ammonia; the pH value of the solution is 8-10; the temperature of the heating reaction is 40-60 ℃ and the time is 2-4 h;
in the step (4), the pH regulator is Na 2 CO 3 Aqueous solutions or ammonia; the pH value of the solution is 8-10; the mass ratio of the phytic acid to the water is 1:5-1:10; the mass ratio of the phytic acid to the phosphorus-silicon hybrid polymeric flame retardant is 2:3-3:2; the temperature of the heating reaction is 40-60 ℃ and the time is 2-4 h.
2. The flame-retardant anti-dripping core-shell particle prepared by the preparation method of claim 1.
3. A flame retardant, anti-drip polylactic acid material comprising the flame retardant, anti-drip core-shell particle of claim 2.
4. The flame retardant, melt drip resistant polylactic acid material according to claim 3, wherein: the preparation method of the flame-retardant anti-dripping polylactic acid material comprises the steps of uniformly mixing PLA and flame-retardant anti-dripping core-shell particles, adding the mixture into a double-screw extruder for extrusion granulation, and performing hot-pressing treatment to obtain the required shape.
5. The flame retardant, melt drip resistant polylactic acid material according to claim 4, wherein: the mass ratio of the flame-retardant anti-dripping core-shell particles to PLA is 1-10%; the melting temperature is 170-190 ℃ and the rotating speed is 200-250rpm.
6. The flame retardant, melt drip resistant polylactic acid material according to claim 5, wherein: the mass ratio of the flame-retardant anti-dripping core-shell particles to PLA is 2-5%.
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| CN107022142A (en) * | 2017-04-20 | 2017-08-08 | 安徽春辉仪表线缆集团有限公司 | A kind of DOPO derivatives grafts siloxanes flame retarding reaction type cable material and preparation method thereof |
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