CN114196040A - Diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant and preparation method and application thereof - Google Patents
Diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant and preparation method and application thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 90
- 239000003063 flame retardant Substances 0.000 title claims abstract description 59
- 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 56
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- -1 melamine aluminum salt Chemical compound 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- 239000004626 polylactic acid Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 29
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- 229920000642 polymer Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 150000001299 aldehydes Chemical class 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 230000007071 enzymatic hydrolysis Effects 0.000 claims 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
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- 238000001746 injection moulding Methods 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
- 229920005586 poly(adipic acid) Polymers 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 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
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- YXHXDEBLSQQHQE-UHFFFAOYSA-N N.N.OP(O)=O Chemical group N.N.OP(O)=O YXHXDEBLSQQHQE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
Abstract
The invention provides a preparation method of a diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant. The flame retardant disclosed by the invention is simple in synthesis process, environment-friendly, good in thermal stability, high in flame retardant efficiency when used in polylactic acid, and capable of effectively inhibiting molten drops of the polylactic acid.
Description
Technical Field
The invention belongs to the technical field of bio-based high polymer flame retardance, and particularly relates to a diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant, and a preparation method and application thereof.
Background
The intumescent flame retardant is the mainstream of the current flame retardant research due to the advantages of high efficiency, environmental protection, good thermal stability, high flame retardant efficiency, good compatibility with high polymers and the like. In order to implement the concept of "green chemistry", researchers have begun to prepare green intumescent flame retardants from biomass materials while pursuing highly efficient integrated intumescent flame retardants.
Lignin is a natural aromatic polymer with large reserves in nature and strong biodegradability and renewability, and is the second largest natural macromolecule next to cellulose. However, except that a small amount of lignin is used for manufacturing chemical products, most of lignin is used as fuel or discharged into rivers, so that great resource waste is caused, and the real value of the lignin is not substantially reflected. The lignin has an aromatic structure and good thermal stability, can generate a coke layer with good compactness in the thermal decomposition process, and can reduce the combustion rate by reducing the diffusion of heat and oxygen, so the lignin can be used as a carbon source of the intumescent flame retardant. The lignin is a highly branched polymer with various functional groups, so that the reactivity of the lignin is very strong, and flame retardant elements such as P, N can be introduced into the molecular structure of the lignin through chemical reaction, thereby further improving the flame retardant efficiency of the lignin.
Diethylenetriamine pentamethylene phosphonic acid (DPPMP) is used as a nontoxic organic acid, is high in quality and low in price, has lower acidity than inorganic acid, contains ammonium phosphonate groups, can be decomposed at high temperature to release ammonia gas and generate phosphonic acid groups, and can be used as an excellent acid source and gas source to be applied to the intumescent flame retardant.
The invention provides a diethylenetriamine penta (methylene phosphonic acid) melamine-modified lignin single-component intumescent flame retardant prepared by taking diethylenetriamine penta (methylene phosphonic acid) as an acid source, lignin as a carbon source and melamine as an air source, which not only can effectively utilize lignin which is a renewable natural polymer to increase the char formation rate of polylactic acid during combustion, but also can fully play a good flame-retardant effect between the lignin and the diethylenetriamine penta (methylene phosphonic acid) melamine salt, and is expected to be applied to the polylactic acid and obtain a good flame-retardant molten drop-preventing effect.
Disclosure of Invention
The invention aims to provide a preparation method of a diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant.
Wherein the structural general formula of the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant is as follows (R is Al3+)：
The preparation method comprises the following steps:
(1) weighing lignin, dissolving the lignin in an alkali solution at room temperature, and obtaining the lignin alkali solution through ultrasonic vibration; magnetically stirring the lignin alkali solution at 70-120 ℃, adding aldehyde, and continuously reacting for 1.0-3.0 h under heat preservation to obtain a lignin aldehyde solution;
(2) adding melamine into deionized water to prepare turbid liquid, magnetically stirring the turbid liquid at 70-120 ℃, adding diethylenetriamine pentamethylene phosphonic acid after the temperature is stable, and continuously performing heat preservation reaction for 0.1-0.5 h to obtain diethylenetriamine pentamethylene phosphonic acid melamine salt;
(3) dripping the lignin aldehyde solution obtained in the step (1) into the step (2), and continuing to keep the temperature and stir for reaction to obtain a modified lignin polymer;
(4) and (3) adding aluminum salt into the modified lignin polymer obtained in the step (3), continuing to keep the temperature and stir for 1.0-3.0 h, aging, then performing vacuum filtration, drying, crushing and sieving the filtered product to obtain a light brown yellow powder product, namely the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant.
The application of the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant in polylactic acid is as follows: the formula design of the toughened flame-retardant polylactic acid composite material comprises the following components: the flame retardant polylactic acid composite material comprises, by weight, 60-80 parts of polylactic acid, 10-20 parts of a flame retardant and 10-20 parts of a toughening agent.
Further, the alkali in the step (1) is one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and OH in the alkali solution-The mass concentration of (A) is 0.1-3 wt%; the lignin is one or more of alkali lignin, enzymolysis lignin, organic lignin and lignosulfonate, and the dosage of the alkali solution is 0.01-0.1 mol/10g lignin.
Further, the aldehyde in the step (2) is one or more of formaldehyde, acetaldehyde and butyraldehyde, the aldehyde is used in an amount of 0.025-0.25mol/10g of lignin, the melamine is used in an amount of 0.05-0.25 mol/10g of lignin, and the stirring speed is 300-600 rpm.
Further, the dosage of the diethylenetriamine pentamethylene phosphonic acid in the step (4) is 0.01 to 0.05 mol/10g of lignin; the reaction temperature is 70-100 ℃, the reaction time is 1-3 h, the aging time is 12-24 h, the drying temperature is 70-100 ℃, the drying time is 12-24 h, and the stirring speed is 300-600 rpm.
Further, in the step (5), the toughening agent is one or a combination of two of polybutylene succinate (PBS), thermoplastic polyurethane elastomer rubber (TPU) and polybutylene adipate terephthalate (PBAT).
The invention has the following remarkable advantages:
(1) the synthesis of the flame retardant is completed in a water phase, the preparation process is simple, green and environment-friendly, and the industrial production is easy to realize.
(2) The lignin is a renewable biomass resource, has low cost, wide source, rich yield, biodegradability and environmental protection, is chemically modified and then applied to the flame retardance of polylactic acid, and provides a new idea for the high-valued utilization of the lignin in the flame retardance field.
(3) The designed and prepared bio-based flame retardant is a three-source-integrated single-component intumescent flame retardant, has good thermal stability, good dispersibility, high flame retardant efficiency, good smoke suppression effect, molten drop prevention and environmental friendliness, does not influence the biodegradation characteristic when added into polylactic acid, and can greatly expand the application of the polylactic acid in the fields of electronic appliances, automobiles, packaging and the like.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a FT-IR diagram of the flame retardant used in example 1;
FIG. 3 is an SEM photograph of the burned carbon layer of the sample bar prepared in application example 1;
FIG. 4 is an SEM photograph of the burned carbon layer of the sample strip prepared in application example 2;
FIG. 5 is an SEM photograph of the burned carbon layer of the sample strip prepared in application example 3;
FIG. 6 is an SEM photograph of the burned carbon layer of the sample bar prepared in comparative example 1;
FIG. 7 is an SEM photograph of the burned carbon layer of the sample strip prepared in comparative example 2.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1:
0.2 g (0.005 mol) of sodium hydroxide is weighed in a beaker, deionized water is added to prepare 0.1 wt% sodium hydroxide solution, then 10g of lignin is added into the sodium hydroxide solution, and the lignin is completely dissolved by ultrasonic vibration. Pouring the dissolved lignin solution into a three-neck flask provided with a magnetic stirrer and a reflux condenser, raising the temperature of a water bath to 70 ℃ under the stirring condition of 300-600 rpm, adding 0.025 mol of formaldehyde after the temperature is stable, and reacting for 1 h to obtain the lignin aldehyde solution. Weighing 6.3 g (0.05 mol) of melamine, adding the melamine into deionized water to prepare white turbid liquid, pouring the white turbid liquid into a three-neck flask provided with a magnetic stirrer and a reflux condenser, raising the temperature of a water bath kettle to 70 ℃ under the stirring condition of 300 plus materials and 600 rpm, adding 5.7 g (0.01 mol) of diethylenetriamine pentamethylene phosphonic acid after the temperature is stable, and continuing to carry out heat preservation reaction for 1 h. Slowly dripping the lignin aldehyde solution into the diethylenetriamine pentamethylene phosphonate by using a separating funnel, and continuously stirring for reaction for 1 h to obtain the modified lignin polymer. 6.8 g (0.02 mol) of aluminum sulfate solution was slowly dropped into the modified lignin polymer solution with a separatory funnel, and the reaction was continued with stirring for 1 hour. And aging the reaction suspension for 12 h, carrying out vacuum filtration, drying the filtered product in an oven at 70 ℃ for 12 h, crushing and sieving with a 200-mesh sieve to obtain a light brown yellow powder product of the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant.
Example 2:
0.56 g (0.01 mol) of potassium hydroxide is weighed in a beaker, deionized water is added to prepare a potassium hydroxide solution with the concentration of 0.2 wt%, then 15 g of lignin is added into the sodium hydroxide solution, and the lignin is completely dissolved by ultrasonic vibration. Pouring the dissolved lignin solution into a three-neck flask provided with a magnetic stirrer and a reflux condenser, raising the temperature of a water bath to 80 ℃ under the stirring condition of 300-600 rpm, adding 0.1 mol of acetaldehyde after the temperature is stable, and reacting for 2 h to obtain the lignin aldehyde solution. Weighing 31.5 g (0.25 mol) of melamine, adding the melamine into deionized water to prepare white turbid liquid, pouring the white turbid liquid into a three-neck flask provided with a magnetic stirrer and a reflux condenser, raising the temperature of a water bath kettle to 70 ℃ under the stirring condition of 300 plus materials and 600 rpm, adding 11.4 g (0.02 mol) of diethylenetriamine pentamethylene phosphonic acid after the temperature is stable, and continuing to carry out heat preservation reaction for 2 hours. Slowly dripping the lignin aldehyde solution into the diethylenetriamine pentamethylene phosphonate by using a separating funnel, and continuously stirring for reaction for 2 hours to obtain the modified lignin polymer. Slowly dropping 18.7 g (0.05 mol) of aluminum nitrate solution into the modified lignin polymer solution by using a separating funnel, continuously stirring and reacting for 2 h, aging the reaction suspension for 12 h, performing vacuum filtration, drying the filtered product in a 70 ℃ oven for 12 h, crushing and sieving by using a 200-mesh sieve to obtain a light brown yellow powder product of the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant.
Example 3:
weighing 2 g (0.1 mol) of sodium hydroxide in a beaker, adding deionized water to prepare a sodium hydroxide solution with the concentration of 3 wt%, then adding 20 g of lignin in the sodium hydroxide solution, and completely dissolving the lignin by ultrasonic vibration. Pouring the dissolved lignin solution into a three-neck flask provided with a magnetic stirrer and a reflux condenser, raising the temperature of a water bath to 90 ℃ under the stirring condition of 300-600 rpm, adding 0.2 mol of butyraldehyde after the temperature is stable, and reacting for 1 h to obtain the lignin aldehyde solution. Weighing 63 g (0.5 mol) of melamine, adding the melamine into deionized water to prepare white turbid liquid, pouring the white turbid liquid into a three-neck flask provided with a magnetic stirrer and a reflux condenser, raising the temperature of a water bath kettle to 70 ℃ under the stirring condition of 300 plus 600 rpm, adding 17.1 g (0.03 mol) of diethylenetriamine pentamethylenephosphonic acid after the temperature is stable, and continuing to perform heat preservation reaction for 3 hours. Slowly dripping the lignin aldehyde solution into the diethylenetriamine pentamethylene phosphonate by using a separating funnel, and continuously stirring for reaction for 3 hours to obtain the modified lignin polymer. Slowly dropping 13.3 g (0.1 mol) of aluminum chloride solution into the modified lignin polymer solution by using a separating funnel, continuously stirring and reacting for 3 hours, aging the reaction suspension for 12 hours, carrying out vacuum filtration, drying the filtered product in a 70 ℃ oven for 12 hours, crushing and sieving with a 200-mesh sieve to obtain a light brown yellow powder product of the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant.
Application example 1:
weighing 10 parts (by weight) of the single-component intumescent flame retardant obtained in the example 1, 10 parts (by weight) of poly (adipic acid)/polybutylene terephthalate (PBAT) and 80 parts (by weight) of polylactic acid, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, and performing injection molding to obtain a flame retardant sample strip (length multiplied by width multiplied by thickness =130 mm multiplied by 10 mm multiplied by 3.2 mm), wherein the vertical combustion test grade of the comparative pure PLA can reach UL 94V-0 grade, the LOI value is increased from 19.7% to 27.1%, the melt flow rate is increased from 22.1 g/10min to 27.1 g/10min, the elongation at break is 105%, the tensile strength is 29.2 MPa, and the residual carbon rate of the flame retardant sample strip after being fully carbonized at 800 ℃ in a muffle furnace is 9.6%.
Application example 2:
weighing 10 parts (by weight) of the single-component intumescent flame retardant obtained in the example 2, 10 parts (by weight) of poly (adipic acid)/polybutylene terephthalate (PBAT) and 80 parts (by weight) of polylactic acid, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, and performing injection molding to obtain a flame retardant sample strip (length multiplied by width multiplied by thickness =130 mm multiplied by 10 mm multiplied by 3.2 mm), wherein the vertical combustion test grade of the comparative pure PLA can reach UL 94V-0 grade, the LOI value is increased from 19.7% to 28.5%, the melt flow rate is increased from 22.1 g/10min to 28.8 g/10min, the elongation at break is 118%, the tensile strength is 27.8 MPa, and the residual carbon rate of the flame retardant sample strip after being fully carbonized at 800 ℃ in a muffle furnace is 9.5%.
Application example 3:
weighing 10 parts (by weight) of the single-component intumescent flame retardant obtained in the embodiment 3, 10 parts (by weight) of poly (adipic acid)/polybutylene terephthalate (PBAT) and 80 parts (by weight) of polylactic acid, stirring and mixing uniformly, extruding and granulating by a double-screw extruder, and performing injection molding to obtain a flame retardant sample strip (length multiplied by width multiplied by thickness =130 mm multiplied by 10 mm multiplied by 3.2 mm), wherein the vertical combustion test grade of the comparative pure PLA can reach UL 94V-0 grade, the LOI value is increased from 19.7% to 29.4%, the melt flow rate is increased from 22.1 g/10min to 27.3 g/10min, the elongation at break is 95%, the tensile strength is 31.5 MPa, and the residual carbon rate of the flame retardant sample strip after being fully carbonized at 800 ℃ in a muffle furnace is 10.7%.
Comparative example 1:
weighing 10 parts (by weight) of modified lignin polymer, 10 parts (by weight) of poly (butylene adipate terephthalate) (PBAT) and 80 parts (by weight) of polylactic acid, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, and performing injection molding to obtain a flame retardant property test sample strip (length multiplied by width multiplied by thickness =130 mm multiplied by 10 mm multiplied by 3.2 mm), wherein the vertical combustion test grade of the sample strip can reach UL 94V-1 grade compared with pure PLA, the LOI value is increased from 19.7% to 25.2%, the melt flow rate is increased from 22.1 g/10min to 25.8 g/10min, the elongation at break is 89%, the tensile strength is 32.1 MPa, and the residual carbon rate of the flame retardant sample strip after being fully carbonized at 800 ℃ in a muffle furnace is 8.7%.
Comparative example 2:
weighing 8 parts (by weight) of modified lignin polymer, 2 parts (by weight) of aluminum sulfate, 10 parts (by weight) of poly adipic acid/butylene terephthalate (PBAT) and 80 parts (by weight) of polylactic acid, stirring and uniformly mixing, extruding and granulating by a double-screw extruder, and performing injection molding to obtain a flame retardant property test sample strip (length multiplied by width multiplied by thickness =130 mm multiplied by 10 mm multiplied by 3.2 mm), wherein compared with pure PLA, the vertical combustion test grade can reach UL 94V-1 grade, the LOI value is increased from 19.7% to 25.8%, the melt flow rate is increased from 22.1 g/10min to 24.9 g/10min, the breaking elongation is 70%, the tensile strength is 38.8 MPa, and the residual carbon rate of the flame retardant sample strip is 8.9% after being fully carbonized at 800 ℃ in a muffle furnace.
From comparative example 1 and comparative example 2, it can be seen that:
(1) the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant has good dispersibility in PLA, high flame retardant efficiency, good smoke suppression effect and obvious molten drop prevention effect, and can achieve excellent flame retardant effect and maintain good mechanical property with less addition.
(2) When the modified lignin polymer is used in PLA alone, the flame retardant efficiency is high, but the phenomenon of melt dripping still exists.
(3) When the modified lignin polymer and aluminum sulfate are added into PLA in a mode of a blend, the melt dripping phenomenon is obviously improved, but the compatibility of the aluminum sulfate and the PLA is too poor, so that the mechanical property of the composite material is reduced.
FIG. 2 is a FT-IR plot of the lignin used in example 1 and the flame retardant prepared. The comparison shows that the fire retardant well retains the basic structure of the lignin. But at 3468 cm-1And 3416 cm-1Has obvious-NH2Characteristic peak, 3210 cm-1Nearby is NH2Peak of bending vibration of 1650 cm-1A stretching vibration peak of C = N bond on the triazine ring appears, and is 1226 cm-1A stretching vibration peak at P = O. 924 cm-1The characteristic absorption peak of (A) is a P-O groupAt 1053 cm-1、855 cm-1The characteristic peak is P-O bond of P-O-C, which indicates that the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant is successfully prepared.
FIGS. 3 to 7 are SEM images of the burned carbon layers of the sample tapes prepared in application examples 1 to 3 and comparative examples 1 to 2, respectively. It can be seen from the figure that the carbon layer of the sample bar prepared in application example 1-3 is uniform and dense after combustion, the holes of the carbon layer of the sample bar prepared in comparative example 1-2 are too many after combustion, and the degree of densification of the carbon layer is increased after the aluminum salt is added, but the carbon layer still cannot play a role in completely blocking the heat source.
In order to make the present invention more comprehensible, the present invention has been described in further detail with reference to specific embodiments, but the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention are within the protection scope of the present invention.
Claims (9)
1. A preparation method of diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant is characterized in that: the method comprises the following steps:
(1) weighing lignin, dissolving the lignin in an alkali solution, and obtaining the lignin alkali solution through ultrasonic vibration; then, magnetically stirring the lignin alkali solution uniformly at 70-120 ℃, adding aldehyde, and continuously reacting for 1.0-3.0 h under heat preservation to obtain a lignin aldehyde solution;
(2) adding melamine into deionized water to prepare turbid liquid, magnetically stirring the turbid liquid at 70-120 ℃, adding diethylenetriamine pentamethylene phosphonic acid after the temperature is stable, and continuously carrying out heat preservation reaction for 0.5-2 h to obtain diethylenetriamine pentamethylene phosphonic acid melamine salt;
(3) dripping the lignin aldehyde solution obtained in the step (1) into the step (2), and continuing to keep the temperature and stir for reaction to obtain a modified lignin polymer;
(4) and (3) adding aluminum salt into the modified lignin polymer obtained in the step (3), continuously keeping the temperature and stirring for 1.0-3.0 h, aging, then carrying out vacuum filtration, drying, crushing and sieving the filtered product to obtain a light brown yellow powder product, namely the diethylenetriamine penta (methylene phosphonic acid) melamine aluminum salt modified lignin single-component intumescent flame retardant.
2. The method of claim 1, wherein: the alkali in the step (1) is one or more of sodium hydroxide, potassium hydroxide and barium hydroxide, and OH in the alkali solution-The mass concentration of (B) is 0.1-5.0 wt%.
3. The method of claim 1, wherein: the lignin in the step (1) is one or more of alkali lignin, enzymatic hydrolysis lignin, organic lignin and lignosulfonate, and the dosage of the alkali solution is 0.01-0.1 mol/10g of lignin.
4. The method of claim 1, wherein: in the step (1), the aldehyde is one or more of formaldehyde, acetaldehyde and butyraldehyde, and the using amount of the aldehyde is 0.025-0.25mol/10g of lignin.
5. The method of claim 1, wherein: in the step (2), the dosage of the diethylenetriamine pentamethylene phosphonic acid is 0.01 to 0.05 mol/10g lignin; the dosage of the melamine in the step (2) is 0.05-0.5 mol/10g of lignin; the stirring speed is as follows: 300-.
6. The method of claim 1, wherein: the aluminum salt in the step (1) is one or more of aluminum nitrate, aluminum chloride and aluminum sulfate, and the dosage of the aluminum salt is as follows: 0.025-0.25mol/10g lignin; the aging time of the reaction solution is 12-24 h, and the drying temperature is 70-100 ℃; stirring speed: 300-.
7. The aluminum salt-modified lignin one-component intumescent flame retardant prepared by the preparation method of any one of claims 1 to 6.
8. The flame-retardant polylactic acid composite material is characterized by comprising, by weight, 60-80 parts of polylactic acid, 10-20 parts of a flame retardant and 10-20 parts of a toughening agent.
9. The flame retardant polylactic acid composite material according to claim 8, wherein the toughening agent is one or two of polybutylene succinate, thermoplastic polyurethane elastomer rubber and polybutylene adipate/terephthalate.
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