CN116041557A - Double-esterified starch flame retardant and preparation method thereof, starch-based flame retardant finishing agent and preparation method and application thereof - Google Patents
Double-esterified starch flame retardant and preparation method thereof, starch-based flame retardant finishing agent and preparation method and application thereof Download PDFInfo
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- CN116041557A CN116041557A CN202211700287.XA CN202211700287A CN116041557A CN 116041557 A CN116041557 A CN 116041557A CN 202211700287 A CN202211700287 A CN 202211700287A CN 116041557 A CN116041557 A CN 116041557A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 123
- 239000008107 starch Substances 0.000 title claims abstract description 123
- 235000019698 starch Nutrition 0.000 title claims abstract description 123
- 239000003063 flame retardant Substances 0.000 title claims abstract description 120
- 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 112
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 42
- 239000004626 polylactic acid Substances 0.000 claims abstract description 42
- 239000004744 fabric Substances 0.000 claims abstract description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- 229920002261 Corn starch Polymers 0.000 claims abstract description 23
- 239000008120 corn starch Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 14
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 14
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000005886 esterification reaction Methods 0.000 claims description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 16
- 235000019270 ammonium chloride Nutrition 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 230000000149 penetrating effect Effects 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002485 combustion reaction Methods 0.000 description 15
- 239000000835 fiber Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ORSVWFJAARXBHC-UHFFFAOYSA-N carbamic acid;phosphoric acid Chemical compound NC(O)=O.OP(O)(O)=O ORSVWFJAARXBHC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003508 chemical denaturation Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/06—Esters of inorganic acids
- C08B31/066—Starch phosphates, e.g. phosphorylated starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/11—Starch or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
-
- 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)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a double-esterified starch flame retardant, a starch-based flame retardant finishing agent, and a preparation method and application thereof, and belongs to the technical field of flame retardants. The double-esterified starch flame retardant is prepared from corn starch, sodium dihydrogen phosphate, disodium hydrogen phosphate and urea, and has the advantages of wide raw material sources, rich and easily obtained raw materials and low cost; the preparation process of the flame retardant is simple, and the using equipment is few; the flame-retardant finishing condition is few, the method is convenient and easy to implement, the flame-retardant effect is good, and the limiting oxygen index of the finished polylactic acid Hadamard fabric is improved from 21.4 to 24.8; meanwhile, the flame retardant can be completely degraded, and environmental pollution is not easy to cause in subsequent treatment.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a double-esterified starch flame retardant, a starch-based flame retardant finishing agent, and a preparation method and application thereof.
Background
Polylactic acid fiber sources are wide, and wastes can be degraded into carbon dioxide and water in the nature, so that the polylactic acid fiber is an ecological fiber which can be continuously developed. However, the inflammability and the combustion dripping property of the polylactic acid fiber cause great potential safety hazards in the production and use processes, so that the flame retardant modification of the polylactic acid fiber is necessary to be studied, and the polylactic acid fiber has great significance for wide application.
The starch has the advantages of low cost, easy obtainment, no pollution, easy degradation and the like, and is widely applied to flame retardant finishing. The phosphate starch is an esterified starch formed by the esterification reaction of hydroxyl groups in the glucose residues of the starch and phosphate; the carbamate starch is prepared by substituting partial hydroxyl groups in glucose residues of starch with carbamate groups, and introducing amide groups into starch macromolecules. The two kinds of esterified starch are singly used, the gelatinization performance and stability of starch slurry are low, the flame retardant effect is poor, and the application is limited to a certain extent.
Disclosure of Invention
The invention aims to provide the di-esterified starch, the starch-based flame retardant finishing agent, the preparation method and the application thereof, and the obtained di-esterified starch has remarkable flame retardant effect, and the flame retardant property of the polylactic acid fabric treated by the di-esterified starch is remarkably improved, so that the combustion property of the polylactic acid fabric can be effectively improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a double-esterified starch flame retardant, which comprises the following steps:
dissolving sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium chloride and urea into water, and mixing the obtained solution with corn starch to obtain starch suspension; the corn starch accounts for 95-105 parts by mass; 9.5 to 10.5 parts of sodium dihydrogen phosphate; 9.5 to 10.5 parts of disodium hydrogen phosphate; 9.5 to 10.5 portions of ammonium chloride; 9.5 to 10.5 portions of urea;
filtering the starch suspension to obtain a filter cake;
drying the filter cake and then carrying out esterification reaction to obtain a di-esterified starch flame retardant; the temperature of the esterification reaction is 128-130 ℃.
Preferably, the esterification reaction time is 110 to 120 minutes.
Preferably, the water content of the dried filter cake is 10-12%.
Preferably, the esterification reaction further comprises: washing, drying, crushing and sieving the esterification reaction product in sequence.
The invention provides the di-esterified starch flame retardant prepared by the preparation method.
The invention provides a preparation method of a starch-based flame retardant finishing agent, which comprises the following steps: mixing 95-105 parts of di-esterified starch flame retardant, 18-20 parts of penetrating agent, 18-20 parts of urea and 1900-2100 parts of water to obtain suspension; carrying out liquid cooling reflux heating on the suspension to gelatinize starch, so as to obtain a starch-based flame retardant finishing agent; the di-esterified starch flame retardant is the di-esterified starch flame retardant of claim 5.
Preferably, the temperature of the condensation reflux heating is 88-90 ℃, and the heat preservation time is 15-20 min.
The invention provides the starch-based flame retardant finishing agent prepared by the preparation method.
The invention provides application of the starch-based flame retardant finishing agent in finishing polylactic acid fabrics.
Preferably, the method for finishing polylactic acid fabric comprises the following steps: placing the polylactic acid fabric into the starch-based flame retardant finishing agent for padding, taking out the polylactic acid fabric, and sequentially pre-drying and baking; the temperature of the pre-drying is 103-105 ℃; the baking temperature is 125-130 ℃.
The invention provides a preparation method of a double-esterified starch flame retardant, which comprises the following steps: dissolving sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium chloride and urea into water, and mixing the obtained solution with corn starch to obtain starch suspension; the corn starch accounts for 95-105 parts by mass; 9.5 to 10.5 parts of sodium dihydrogen phosphate; 9.5 to 10.5 parts of disodium hydrogen phosphate; 9.5 to 10.5 portions of ammonium chloride; 9.5 to 10.5 portions of urea; filtering the starch suspension to obtain a filter cake; drying the filter cake and then carrying out esterification reaction to obtain a di-esterified starch flame retardant; the temperature of the esterification reaction is 128-130 ℃.
The invention adopts a double-esterification method to prepare the double-esterification starch flame retardant, and phosphorus-nitrogen-containing starch-based flame retardant is prepared by introducing phosphate groups and amino groups into starch macromolecules.
The invention adopts the phosphate-carbamate di-esterified starch, namely the phosphate-carbamate starch, which can obviously reduce the gelatinization temperature of the starch, improve the stability of the paste, and improve the adhesion performance of polylactic acid fibers, thereby obviously improving the flame retardance of the finished polylactic acid Hadamard fabric.
The double-esterified starch flame retardant has the advantages of both phosphorus flame retardants and nitrogen flame retardants, and can generate acidic substances such as pyrophosphoric acid, polyphosphoric acid and the like which promote the polymer to form carbon in the combustion degradation process, so that a compact continuous carbon layer is formed on the surface of the material, the outside oxygen and heat are isolated, and the reaction of free radicals is prevented; and the phosphorus-containing free radicals generated in the combustion process can capture the external free radicals, so that the whole combustion process is delayed, and the gas-phase flame retardant effect is achieved. Moreover, the catalyst is decomposed by heating and then NH is released in the combustion process 3 、NO、N 2 And a large amount of inert gases such as O and the like can play a role in diluting the concentration of oxygen on the surface of the matrix and the concentration of combustible volatile matters to a certain extent, so that a flame-retardant effect is achieved. Therefore, compared with a single phosphorus-based or nitrogen-based flame retardant, the phosphorus-nitrogen-containing double-modified starch flame retardant can remarkably improve the flame retardant effect of polylactic acid fabrics.
Compared with the traditional inorganic flame retardant, the double-esterified starch flame retardant has good biocompatibility, has good adhesiveness to polylactic acid fibers, and can be completely biodegraded. Is a brand new natural polymer flame retardant finishing agent.
In summary, the di-esterified starch flame retardant is prepared from corn starch, sodium dihydrogen phosphate, disodium hydrogen phosphate and urea, and has the advantages of wide raw material sources, abundant and easily obtained raw materials and low cost; the preparation process of the flame retardant is simple, and the using equipment is few; the flame-retardant finishing condition is few, the method is convenient and easy to implement, the flame-retardant effect is good, and the limiting oxygen index of the finished polylactic acid Hadamard fabric is improved from 21.4 to 24.8; meanwhile, the flame retardant can be completely degraded, and environmental pollution is not easy to cause in subsequent treatment.
Drawings
FIG. 1 is an infrared spectrum of a di-esterified starch flame retardant prepared in example 1 with corn starch;
FIG. 2 is a scanning electron microscope image of corn starch;
FIG. 3 is a scanning electron microscope image of the carbamate starch flame retardant prepared in comparative example 1;
FIG. 4 is a scanning electron microscope image of the di-esterified starch flame retardant prepared in example 1.
Detailed Description
The invention provides a preparation method of a double-esterified starch flame retardant, which comprises the following steps:
dissolving sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium chloride and urea into water, and mixing the obtained solution with corn starch to obtain starch suspension; the corn starch accounts for 95-105 parts by mass; 9.5 to 10.5 parts of sodium dihydrogen phosphate; 9.5 to 10.5 parts of disodium hydrogen phosphate; 9.5 to 10.5 portions of ammonium chloride; 9.5 to 10.5 portions of urea;
filtering the starch suspension to obtain a filter cake;
drying the filter cake and then carrying out esterification reaction to obtain a di-esterified starch flame retardant; the temperature of the esterification reaction is 128-130 ℃.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
Sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium chloride and urea are dissolved in water, and the obtained dissolution liquid is mixed with corn starch to obtain starch suspension.
In the invention, the corn starch accounts for 95-105 parts by mass; 9.5 to 10.5 parts of sodium dihydrogen phosphate; 9.5 to 10.5 parts of disodium hydrogen phosphate; 9.5 to 10.5 portions of ammonium chloride; 9.5 to 10.5 portions of urea; the water is preferably 90 to 110 parts. Further, the corn starch is preferably 98 to 102 parts, the sodium dihydrogen phosphate is preferably 9.8 to 10.2 parts, the disodium hydrogen phosphate is preferably 9.8 to 10.2 parts, the ammonium chloride is preferably 9.8 to 10.2 parts, the urea is preferably 9.8 to 10.2 parts, and the water is more preferably 95 to 105 parts. In the present invention, the water is preferably deionized water.
In the present invention, the mixing of the obtained dissolution liquid with corn starch is preferably adding corn starch to the dissolution liquid. In the invention, after corn starch is added, the invention preferably stirs for 25-30 min at 48-50 ℃ to obtain starch suspension. The invention is stirred at 48-50 ℃ for 25-30 min to swell the starch and fully mix with the reaction agent.
After the starch suspension is obtained, the invention filters the starch suspension to obtain a filter cake.
In the present invention, the filtration is preferably suction filtration.
After a filter cake is obtained, the filter cake is dried and subjected to esterification reaction to obtain the di-esterified starch flame retardant; the temperature of the esterification reaction is 128-130 ℃.
In the invention, the temperature of the drying is preferably 48-52 ℃, the time of the drying is not particularly required, and the water content of the dried filter cake is preferably 10-12%. The invention controls the water content of the filter cake to be 10-12%, and aims to ensure that the water content is within the range, the reaction agent can be fully contacted with the starch, and meanwhile, the hydrolysis side reaction of the esterified starch caused by excessive water content is avoided.
In the present invention, the time of the esterification reaction is preferably 110 to 120 minutes. In the esterification reaction process, starch macromolecules are subjected to phosphoric acid esterification reaction with orthophosphate under the catalysis of urea, and simultaneously, are reacted with amino groups to produce carbamate starch.
After the esterification reaction is completed, the esterification reaction product is preferably washed, dried, crushed and sieved in sequence to obtain the double-esterified starch flame retardant.
In the present invention, the washing is preferably rinsing 2 to 3 times with deionized water; the temperature of the drying is preferably 48-50 ℃; the screening is preferably a 65 mesh screen.
The invention adopts a double-esterification method to prepare the double-esterification starch flame retardant, and phosphorus-nitrogen-containing starch-based flame retardant is prepared by introducing phosphate groups and amino groups into starch macromolecules.
The invention provides the di-esterified starch flame retardant prepared by the preparation method. The double-esterified starch flame retardant has the advantages of both phosphorus flame retardants and nitrogen flame retardants, and can generate acidic substances such as pyrophosphoric acid, polyphosphoric acid and the like which promote the polymer to form carbon in the combustion degradation process, so that a compact continuous carbon layer is formed on the surface of the material, the outside oxygen and heat are isolated, and the reaction of free radicals is prevented; and the phosphorus-containing free radicals generated in the combustion process can capture the external free radicals, so that the whole combustion process is delayed, and the gas-phase flame retardant effect is achieved. Moreover, the catalyst is decomposed by heating and then NH is released in the combustion process 3 、NO、N 2 And a large amount of inert gases such as O and the like can play a role in diluting the concentration of oxygen on the surface of the matrix and the concentration of combustible volatile matters to a certain extent, so that a flame-retardant effect is achieved. Therefore, compared with the single phosphorus-based or nitrogen-based flame retardant,the flame retardant effect of the polylactic acid fabric can be obviously improved.
The invention provides a preparation method of a starch-based flame retardant finishing agent, which comprises the following steps: mixing 95-105 parts of di-esterified starch flame retardant, 18-20 parts of penetrating agent, 18-20 parts of urea and 1900-2100 parts of water to obtain suspension; carrying out liquid cooling reflux heating on the suspension to gelatinize starch, so as to obtain a starch-based flame retardant finishing agent; the di-esterified starch flame retardant is the di-esterified starch flame retardant of claim 5.
In the invention, the temperature of the condensing reflux heating is preferably 88-90 ℃, and the heat preservation time is preferably 15-20 min.
The invention has no special requirements on the type of the penetrating agent, and the penetrating agent well known in the art can be adopted. In the invention, the urea has the function of promoting the swelling of polylactic acid fibers in hot water so as to facilitate the diffusion and permeation of macromolecules of the double-esterified starch flame retardant to the polylactic acid fibers, and the loading rate of the flame retardant is improved so as to further enhance the flame retardant effect of the polylactic acid Hadamard fabric.
The invention provides the starch-based flame retardant finishing agent prepared by the preparation method.
The invention also provides application of the starch-based flame retardant finishing agent in finishing polylactic acid fabrics. In the present invention, the polylactic acid fabric preferably includes polylactic acid hadamard.
In the present invention, the method of finishing polylactic acid fabric preferably comprises the steps of: placing the polylactic acid fabric into the starch-based flame retardant finishing agent for padding, taking out the polylactic acid fabric, and sequentially pre-drying and baking; the temperature of the pre-drying is 103-105 ℃; the baking temperature is 125-130 ℃.
In the present invention, the padding ratio of the padding is preferably 200%. In the invention, the time for pre-drying is preferably 8-10 min; the baking time is preferably 2 to 3 minutes. The pre-drying stage is to remove water as much as possible to bring side reaction, namely hydrolysis reaction, to the esterification reaction; and then baking at 125-130 ℃ to react with the fiber, thereby producing washable flame retardant effect.
The unesterified starch flame retardant, the starch-based flame retardant finish, and the preparation method and application thereof provided by the invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
Dissolving 10 parts of sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium chloride and urea in 100 parts of deionized water to prepare a solution, and adding corn starch into the solution to prepare a suspension; heating the suspension in 50deg.C water bath, and stirring with magnetic stirrer for 30min; filtering with a suction filter to obtain a filter cake and weighing;
it was dried in an oven at 50℃until the water content was 10%, and then reacted at 130℃for 2 hours. Washing the product with deionized water for 2-3 times, then drying at a low temperature in a 50 ℃ oven, crushing and sieving with a 65-mesh sieve to obtain the powdery di-esterified starch flame retardant.
Comparative example 1
Dissolving 10 parts of ammonium chloride and urea in 100 parts of deionized water respectively to prepare a solution, and adding corn starch into the solution to prepare a suspension; heating the suspension in 50deg.C water bath, and stirring with magnetic stirrer for 30min; filtering with a suction filter to obtain a filter cake and weighing;
the mixture was placed in an oven at 50℃to a moisture content of 10% and then reacted at 130℃for 2 hours. Washing the product with deionized water for 2-3 times, then drying at a low temperature in a 50 ℃ oven, crushing and sieving with a 65-mesh sieve to obtain the powdery carbamate starch flame retardant.
The flame retardants prepared in the above example 1 and comparative example 1 were characterized and their physicochemical properties were analyzed.
FIG. 1 is an infrared spectrum of a di-esterified starch flame retardant prepared in example 1 and corn starch. As shown in FIG. 1, the di-esterified starch flame retardant is 3500-3200 cm compared with the original starch -1 Region v O-H 1600cm -1 The delta OH band in the vicinity is narrowed, the peak intensity is weakened, and the change is easy to observe in an infrared spectrogramIt was observed that the partial hydroxyl groups in the starch molecule are consumed by the esterification reaction, resulting in a reduced number of O-H bonds. In addition, the double esterification is carried out at 1750cm -1 Near carbonyl stretching vibration absorption peak v C＝O It is possible that during grafting, a large number of hydroxyl groups participate in the reaction to convert OH bonds to c=o bonds. Furthermore, at 1175cm -1 1116-1007 cm -1 The spectral peak groups of the stretching vibration of the C-N bond and the P= O, P-O bond are also respectively shown. The above changes indicate that amino and phosphate flame-retardant functional groups are introduced into natural starch macromolecules after double esterification modification.
Fig. 2 is a scanning electron microscope image of corn starch, and fig. 3 is a scanning electron microscope image of the urethane starch flame retardant prepared in comparative example 1; FIG. 4 is a scanning electron microscope image of the di-esterified starch flame retardant prepared in example 1. As can be seen from FIG. 2, the natural corn starch particles are mostly polygonal, smooth in surface, regular in shape, small in particle size and mostly in the range of 10-15 μm. As can be seen from fig. 3, the nitrogen-containing single esterified starch particles prepared in comparative example 1 of the present invention were not significantly different from the native starch, indicating a lower degree of denaturation. In contrast, in fig. 4, the phosphorus-nitrogen containing di-esterified starch flame retardant prepared in example 1 of the present invention has particles that are significantly changed compared with natural starch, and the surface of some particles is damaged and perforated, and the morphology and structure of the surface chemically modified starch particles are damaged to some extent. At the same time, some binding phenomenon occurs between the particles, because the chemical denaturation leads to an increase in the polarity of the surface of the starch particles, and thus the inter-particle interactions are enhanced as a result. The change is favorable for gelatinization of starch particles to form stable finishing liquid so as to improve the adhesion effect and flame-retardant finishing effect on polylactic acid fibers.
Application example 1
The raw materials comprise the following components in parts by mass: 100 parts of di-esterified starch flame retardant; 20 parts of penetrating agent; 20 parts of urea; 2000 parts of deionized water.
Dissolving a di-esterified starch flame retardant, a penetrating agent and urea in deionized water to prepare a suspension, transferring the suspension into a three-neck flask, placing the flask in a constant-temperature magnetic stirrer, connecting a condensation reflux device, and stirring for 20min at 90 ℃ to gelatinize the starch to prepare the flame retardant finishing agent.
Taking out the product, performing flame-retardant finishing on the polylactic acid fabric, adopting a padding treatment method, wherein the padding rate is 200%, putting the treated fabric into a baking oven at 105 ℃ for 10min, and then putting the treated fabric into a baking oven at 130 ℃ for baking for 3min to obtain the flame-retardant treated polylactic acid fabric.
Comparative application example 1
Is polylactic acid fabric which is not subjected to flame retardant finishing.
Comparative application example 2
The raw materials comprise the following components in parts by mass: 100 parts of the carbamate starch flame retardant of the comparative example 1; 20 parts of penetrating agent; 20 parts of urea; 2000 parts of deionized water.
Dissolving carbamate starch fire retardant, penetrant and urea in deionized water to prepare suspension, transferring to a three-neck flask, placing the flask in a constant-temperature magnetic stirrer, connecting a condensing reflux device, stirring for 20min at 90 ℃ to gelatinize starch, and preparing the flame retardant finishing agent.
Taking out the product, performing flame-retardant finishing on the polylactic acid fabric, adopting a padding treatment method, wherein the padding rate is 200%, putting the treated fabric into a baking oven at 105 ℃ for 10min, and then putting the treated fabric into a baking oven at 130 ℃ for baking for 3min to obtain the flame-retardant treated polylactic acid fabric.
Limiting oxygen index tests were performed on the polylactic acid fabrics treated with the flame retardants of the respective application examples and comparative application examples. The limiting oxygen index was measured by the oxygen index method of the textile combustion performance test of GB/T5454-1997, and the results are shown in Table 1.
Table 1 limiting oxygen index of application example and comparative application example
| Test case | Limit ofOxygen index (%) |
| Application example 1 | 24.8 |
| Comparative application example 1 | 21.4 |
| Comparative application example 2 | 22.5 |
As can be seen from the test results in Table 1, in comparative application example 1, the Hadamard fabric of the pure polylactic acid fiber has a lower limiting oxygen index of 21.4%, indicating higher flammability. In comparative application example 2, the limit oxygen index of the polylactic acid Hadamard finished by the urethane monoesterified starch is improved to 22.5%, which shows that the flame retardance is improved. This is because nitrogen-containing groups are introduced in the monoesterification modification, and NH is released after thermal decomposition during combustion 3 、NO、N 2 And a large amount of inert gases such as O and the like can play a role in diluting the concentration of oxygen on the surface of the matrix and the concentration of combustible volatile matters to a certain extent, so that a flame-retardant effect is achieved. However, in comparative application example 2, the improvement of limiting oxygen index was not significant, indicating that the improvement of flame retardancy was not significant. This is because the above-mentioned gas does not have a high flame retardant efficiency when used alone, although it has a certain dilution effect on the oxygen concentration on the surface of the substrate and the concentration of the flammable volatile matters, thereby having a flame retardant effect.
In application example 1, the limit oxygen index of the polylactic acid hadamard fabric flame-retardant finished by the double-esterified starch reaches 24.8%, which is further improved compared with comparative application example 2, because the double-esterified starch flame retardant has the flame-retardant groups containing nitrogen and phosphorus at the same time. Acidic substances such as pyrophosphoric acid, polyphosphoric acid and the like which promote the formation of carbon of the polymer can be generated in the combustion degradation process, so that a compact continuous carbon layer is formed on the surface of the material, outside oxygen and heat are isolated, the reaction of free radicals is prevented, and in addition, the phosphorus-containing free radicals generated in the combustion process can capture the outside free radicals, so that the whole combustion process is delayed. Therefore, the double-esterified starch flame retardant disclosed by the invention can have the functions of condensed image phase flame retardance and gas phase flame retardance, and is a main reason for good flame retardance on polylactic acid Hadamard fabrics.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the di-esterified starch flame retardant is characterized by comprising the following steps of:
dissolving sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium chloride and urea into water, and mixing the obtained solution with corn starch to obtain starch suspension; the corn starch accounts for 95-105 parts by mass; 9.5 to 10.5 parts of sodium dihydrogen phosphate; 9.5 to 10.5 parts of disodium hydrogen phosphate; 9.5 to 10.5 portions of ammonium chloride; 9.5 to 10.5 portions of urea;
filtering the starch suspension to obtain a filter cake;
drying the filter cake and then carrying out esterification reaction to obtain a di-esterified starch flame retardant; the temperature of the esterification reaction is 128-130 ℃.
2. The method according to claim 1, wherein the esterification reaction time is 110 to 120 minutes.
3. The method according to claim 1, wherein the water content of the dried cake is 10 to 12%.
4. The method according to claim 1, wherein the esterification reaction further comprises: washing, drying, crushing and sieving the esterification reaction product in sequence.
5. The di-esterified starch flame retardant prepared by the preparation method of any one of claims 1 to 4.
6. The preparation method of the starch-based flame retardant finishing agent is characterized by comprising the following steps of: mixing 95-105 parts of di-esterified starch flame retardant, 18-20 parts of penetrating agent, 18-20 parts of urea and 1900-2100 parts of water to obtain suspension; carrying out liquid cooling reflux heating on the suspension to gelatinize starch, so as to obtain a starch-based flame retardant finishing agent; the di-esterified starch flame retardant is the di-esterified starch flame retardant of claim 5.
7. The method according to claim 6, wherein the temperature of the condensing reflux heating is 88-90 ℃ and the heat preservation time is 15-20 min.
8. The starch-based flame retardant finish prepared by the preparation method of claim 6 or 7.
9. Use of the starch-based flame retardant finish of claim 8 for finishing polylactic acid fabrics.
10. The use according to claim 9, characterized in that the method of finishing polylactic acid fabric comprises the steps of: placing the polylactic acid fabric into the starch-based flame retardant finishing agent for padding, taking out the polylactic acid fabric, and sequentially pre-drying and baking; the temperature of the pre-drying is 103-105 ℃; the baking temperature is 125-130 ℃.
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| CN102154851A (en) * | 2011-06-03 | 2011-08-17 | 江西博大化工有限公司 | Phosphate starch printing paste and preparation method thereof |
| CN102477100A (en) * | 2010-11-23 | 2012-05-30 | 兰州瑞特变性淀粉科技有限公司 | Esterification-etherification dual-modified starch and solid phase preparation method thereof |
| CN106496975A (en) * | 2016-09-29 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof |
| CN110511289A (en) * | 2019-08-23 | 2019-11-29 | 安徽工程大学 | A kind of dual esterification starch slurry and preparation method thereof with low surface tension |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102477100A (en) * | 2010-11-23 | 2012-05-30 | 兰州瑞特变性淀粉科技有限公司 | Esterification-etherification dual-modified starch and solid phase preparation method thereof |
| CN102154851A (en) * | 2011-06-03 | 2011-08-17 | 江西博大化工有限公司 | Phosphate starch printing paste and preparation method thereof |
| CN106496975A (en) * | 2016-09-29 | 2017-03-15 | 中国科学院宁波材料技术与工程研究所 | A kind of polylactic acid/starch intumescent flame-retardant composite and preparation method thereof |
| CN110511289A (en) * | 2019-08-23 | 2019-11-29 | 安徽工程大学 | A kind of dual esterification starch slurry and preparation method thereof with low surface tension |
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