CN115449172A - Degradable flame-retardant plastic profile - Google Patents
Degradable flame-retardant plastic profile Download PDFInfo
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- CN115449172A CN115449172A CN202211247014.4A CN202211247014A CN115449172A CN 115449172 A CN115449172 A CN 115449172A CN 202211247014 A CN202211247014 A CN 202211247014A CN 115449172 A CN115449172 A CN 115449172A
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- 229920003023 plastic Polymers 0.000 title claims abstract description 62
- 239000004033 plastic Substances 0.000 title claims abstract description 62
- 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 30
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000001913 cellulose Substances 0.000 claims abstract description 49
- 229920002678 cellulose Polymers 0.000 claims abstract description 49
- 240000007087 Apium graveolens Species 0.000 claims abstract description 43
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 claims abstract description 43
- 235000010591 Appio Nutrition 0.000 claims abstract description 43
- 229920002472 Starch Polymers 0.000 claims abstract description 36
- 229940100445 wheat starch Drugs 0.000 claims abstract description 36
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229940080818 propionamide Drugs 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 33
- 239000012153 distilled water Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- URQMEZRQHLCJKR-UHFFFAOYSA-N 3-Methyl-5-propyl-2-cyclohexen-1-one Chemical compound CCCC1CC(C)=CC(=O)C1 URQMEZRQHLCJKR-UHFFFAOYSA-N 0.000 claims description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 238000011085 pressure filtration Methods 0.000 claims description 3
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 27
- 244000005700 microbiome Species 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002689 soil Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- -1 cerium ions Chemical class 0.000 abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 abstract description 5
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000137 polyphosphoric acid Polymers 0.000 abstract description 5
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 235000011187 glycerol Nutrition 0.000 abstract 6
- 230000000052 comparative effect Effects 0.000 description 30
- 238000004132 cross linking Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229960001484 edetic acid Drugs 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KZNIFHPLKGYRTM-UHFFFAOYSA-N apigenin Chemical compound C1=CC(O)=CC=C1C1=CC(=O)C2=C(O)C=C(O)C=C2O1 KZNIFHPLKGYRTM-UHFFFAOYSA-N 0.000 description 2
- 229940117893 apigenin Drugs 0.000 description 2
- XADJWCRESPGUTB-UHFFFAOYSA-N apigenin Natural products C1=CC(O)=CC=C1C1=CC(=O)C2=CC(O)=C(O)C=C2O1 XADJWCRESPGUTB-UHFFFAOYSA-N 0.000 description 2
- 235000008714 apigenin Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/12—Preparation of cellulose esters of organic acids of polybasic organic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/22—Post-esterification treatments, including purification
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a degradable flame-retardant plastic profile, which belongs to the technical field of plastic profile production and comprises the following raw materials in percentage by weight: 30-35% of polyvinyl alcohol, 25-30% of wheat starch, 12-16% of glycerol, 6-8% of glycerol, 3-7% of urea and 15-22% of grafted cellulose. Glutaric anhydride is added to increase the chain of the celery cellulose, so that the interface bonding strength of the celery cellulose and other atoms is improved; introducing propionamide to cooperate with cerium ions to react with diphenylphosphinic chloride, so that substances such as metaphosphoric acid and polyphosphoric acid are released when the fiber is heated and decomposed, and the cellulose is catalyzed to dehydrate and form carbon, thereby achieving the effect of flame retardance or combustion slowing; glycerin and glycerol are added, and the glycerin destroys most of lattice structures of the wheat starch, promotes the growth of microorganisms in soil and accelerates the degradation speed of the plastic section; the glycerol can penetrate into the wheat starch molecules, so that the distance between the wheat starch molecules is increased, and the tensile strength of the section bar is increased.
Description
Technical Field
The invention belongs to the technical field of plastic profile production, and particularly relates to a degradable flame-retardant plastic profile.
Background
The plastic is a material synthesized or polymerized by a condensation reaction by using a monomer raw material, and is a synthetic high molecular compound. In daily life, plastic products have penetrated the aspects of our life, and the wide application of various plastic products such as plastic shopping bags, plastic cups, agricultural films, plastic containers, plastic components and the like brings great convenience to people, but the plastic products face the problem which is difficult to overcome in the process of high-speed development, for example, the plastic is difficult to degrade under natural conditions, and serious white pollution is brought to soil; most plastic profiles in widespread use are flammable or combustible and in the event of a fire they will become the fuse leading to a serious fire.
Disclosure of Invention
The invention aims to provide a degradable flame-retardant plastic profile, which is added with glutaric anhydride to increase a celery cellulose chain and improve the interface bonding strength of celery cellulose and other atoms; introducing propionamide to cooperate with cerium ions to react with diphenylphosphinic chloride, so that substances such as metaphosphoric acid and polyphosphoric acid are released when the fiber is heated and decomposed, and cellulose is catalyzed to dehydrate and form carbon, thereby achieving the effect of flame retardance or combustion slowing; glycerol and glycerol are added, and the glycerol destroys most of lattice structures of the wheat starch, promotes the growth of microorganisms in soil and accelerates the degradation speed of the plastic section; the glycerol can penetrate into the wheat starch molecules, so that the distance between the wheat starch molecules is increased, and the tensile strength of the section bar is increased.
The technical problems to be solved by the invention are as follows: shorten the degradation period of the plastic section and improve the flame retardance.
The purpose of the invention can be realized by the following technical scheme:
a degradable flame-retardant plastic profile comprises the following raw materials in percentage by weight:
further, the preparation method of the degradable flame-retardant plastic profile comprises the following steps: adding deionized water into polyvinyl alcohol until the polyvinyl alcohol is completely dissolved, stirring at a controlled temperature, adding wheat starch, glycerol, urea and glycerol for gelatinization, ultrasonically oscillating, adding grafted cellulose, continuously and mechanically stirring to obtain a plastic raw material liquid, controlling the temperature of the plastic raw material liquid to 117-123 ℃, mixing for 8-12min, taking out the mixed material, extruding and molding, cooling and molding at a vacuum negative pressure, uniformly drawing the molded section by a tractor, and cutting at a fixed length by a cutting machine to obtain a degradable flame-retardant plastic section; the glycerol destroys most of the lattice structure of the wheat starch, so that the wheat starch and the cellulose chain are crosslinked, and because the wheat starch is easy to degrade, a hole structure is easy to form in the crosslinking process with the cellulose chain, a carbon source is provided for the growth of microorganisms in soil, in addition, the microorganisms absorb part of the glycerol acting on the wheat starch, the glycerol accelerates the growth of the microorganisms, and further accelerates the degradation speed of the microorganisms on the plastic section; the glycerol permeates into the hydroxyl groups in the wheat starch to react, so that the distance between the wheat starch molecules is increased, and the urea is used as a cross-linking agent, so that the cross-linking degree of a reaction system is improved, and the relative sliding between the molecules under the action of external force is limited, so that the tensile strength of the profile is increased.
Further, the stirring temperature is 82-95 ℃, the stirring time is 1-1.5h, the gelatinization time is 1.5-2h, the ultrasonic oscillation time is 0.5-0.8h, and the sealing and drying temperature and time are respectively 20-25 ℃ and 46-50h.
Further, the grafted cellulose is prepared by the following method:
s1, weighing celery, crushing and sieving the celery, extracting the sieved celery with distilled water for 7-8 hours, washing, filtering and drying the celery after extraction is finished to obtain celery powder, sequentially adding a 3% hydrogen peroxide solution, ethylene diamine tetraacetic acid and magnesium sulfate into the celery powder, stirring the mixture by a temperature-controlled machine, washing the mixture with distilled water and filtering the mixture under reduced pressure for 1-2 hours, and drying residues at room temperature to constant weight to obtain celery cellulose;
s2, weighing glutaric anhydride, fully melting, sequentially adding a catalyst and the celery cellulose prepared in the step S1, and uniformly stirring at controlled temperature;
and S3, controlling the temperature to be 45-50 ℃ under the protection of nitrogen, sequentially adding distilled water, cerium nitrate and propionamide, uniformly stirring, then adding an acid-binding agent and diphenyl hypophosphoryl chloride, controlling the temperature in an ice bath for reaction, and then heating for reaction to obtain the grafted cellulose.
Further, in the step S1, the weight ratio of celery to 3% hydrogen peroxide solution to ethylenediaminetetraacetic acid to magnesium sulfate is 100-140:120-160:15-19:8-10, the ethylene diamine tetraacetic acid and the magnesium sulfate are used as the stabilizing agents of the hydrogen peroxide solution, which is beneficial to the stable reaction and keeps better product quality.
Further, the sieving specification in the step S1 is 100 meshes, the speed is controlled to be 105-125rpm during mechanical stirring, the temperature is controlled to be 50-70 ℃, and the stirring time is 1.5-2 hours.
Further, the weight ratio of glutaric anhydride, catalyst, celery cellulose, distilled water, cerium nitrate, propionamide, acid binding agent and diphenyl phosphorus oxychloride in steps S2 and S3 is 20-40:2-8:5-11:20-40:2-6:3-7:2-4:2-6, preferably, introducing nitrogen to react for 2-3 hours under normal pressure before adding glutaric anhydride, and then reacting for 6-8 hours under reduced pressure, so as to remove moisture generated in the reaction and accelerate the reaction rate; glutaric anhydride replaces hydroxyl in celery fiber, a hydrogen bond structure of the celery fiber is damaged, the length of a cellulose chain is increased, the interface bonding strength of the celery fiber and other atoms is further improved, propionamide is introduced to be matched with cerium ions to react with diphenylphosphinic chloride, N and P elements are successfully grafted on the surface of the celery fiber, substances such as metaphosphoric acid, polyphosphoric acid and the like are released when the fiber is heated and decomposed, and the cellulose is catalyzed to be dehydrated into carbon, when the grafted fiber is pyrolyzed in the presence of fire, substances such as micromolecule volatile matters, coke and the like can be generated, and the rapid diffusion of heat on the surface of the fiber is blocked, so that the flame-retardant or combustion-slowing effect is achieved.
Further, the stirring temperature in step S2 is 170-190 ℃.
Further, in the step S3, the temperature and the time in the ice bath are respectively 0-1 ℃ and 7-9h, and the temperature and the time of the heating reaction are respectively 55-65 ℃ and 5-6h.
Further, the catalyst in step S2 is concentrated sulfuric acid, and the acid-binding agent in step S3 is diisopropylethylamine.
The invention has the beneficial effects that:
(1) Glutaric anhydride is added into the prepared plastic section to replace hydroxyl in the celery fiber, and the glutaric anhydride and the hydroxyl are combined in a covalent bond form, so that the hydrogen bond structure of the celery fiber is damaged, a new amorphous area is formed, the polarity of the surface of the celery fiber is reduced, the length of a cellulose chain is increased, and the interface bonding strength of the celery fiber and other atoms is further improved; the propionamide reacts with water to form acrylamide, the acrylamide is grafted on the surface of celery fiber under the initiation of cerium ions and then reacts with diphenylphosphinic chloride, N and P elements are successfully grafted on the surface of the celery fiber, so that substances such as metaphosphoric acid and polyphosphoric acid are released when the fiber is heated and decomposed, and cellulose is catalyzed to be dehydrated into carbon, when the grafted fiber is subjected to pyrohydrolysis, substances such as small molecular volatile matters and coke are generated, and the released gas is coated by a coke carbon layer on the surface of the fiber and cannot be released to the outside to form a bubbling carbon layer and then is attached to the surface of the fiber, so that the rapid diffusion of the heat on the surface of the fiber is further blocked, the transfer flow of the surface of the fiber and the external air is blocked, and the heat exchange is further blocked, thereby the flame-retardant or combustion-slowing effect is achieved.
(2) The glycerol is added, the glycerol plasticizes the wheat starch, most lattice structures of the wheat starch are damaged, strong interaction exists between the wheat starch and a cellulose chain, crosslinking occurs, a hole structure is formed in the crosslinking process of the wheat starch and the cellulose chain due to the fact that the wheat starch is easy to degrade, a carbon source is provided for the growth of microorganisms, the microorganisms absorb part of the glycerol which acts on the wheat starch, the growth of the microorganisms is accelerated by the micromolecular glycerol, and the degradation speed of the plastic section is accelerated;
(3) The invention adds the glycerol to permeate into the wheat starch molecules to react with the hydroxyl in the wheat starch, reduces the number of the original hydroxyl in the system, and simultaneously increases the distance between the wheat starch molecules, and the urea is used as a cross-linking agent, thereby improving the cross-linking degree of the wheat starch, the polyvinyl alcohol and the glycerol, limiting the relative sliding among the molecules under the action of external force, and further increasing the tensile strength of the section.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation of the grafted cellulose comprises the following steps:
s1, weighing 100 parts by weight of celery, crushing, sieving with a 100-mesh sieve, extracting the sieved celery with distilled water for 7.5 hours, washing, filtering, and drying after extraction is finished to obtain celery powder, sequentially adding 120 parts by weight of 3% hydrogen peroxide solution, 15 parts by weight of ethylenediamine tetraacetic acid and 8 parts by weight of magnesium sulfate into the celery powder, controlling the temperature at 60 ℃, mechanically stirring at the rotating speed of 105rpm for 1.8 hours, washing with distilled water, carrying out reduced pressure filtration for 2 hours, and drying residues at room temperature to constant weight to obtain apigenin;
s2, weighing 20 parts by weight of glutaric anhydride, fully melting, sequentially adding 2 parts by weight of concentrated sulfuric acid and 5 parts by weight of the celery cellulose prepared in the step S1, and controlling the temperature to be 170 ℃ and uniformly stirring;
and S3, controlling the temperature to be 50 ℃ under the protection of nitrogen, sequentially adding 20 parts by weight of distilled water, 2 parts by weight of cerium nitrate and 3 parts by weight of propionamide, uniformly stirring, then adding 2 parts by weight of diisopropylethylamine and 2 parts by weight of diphenyl hypophosphite, controlling the temperature to be 0 ℃ in ice bath, reacting for 7 hours, and then heating to 55 ℃ and reacting for 5 hours to obtain the grafted cellulose.
Example 2
The preparation of the grafted cellulose comprises the following steps:
step S1, weighing 120 parts by weight of celery, crushing, sieving with a 100-mesh sieve, extracting the sieved celery with distilled water for 7.5 hours, washing, filtering, and drying after extraction is finished to obtain celery powder, sequentially adding 140 parts by weight of 3% hydrogen peroxide solution, 17 parts by weight of ethylenediamine tetraacetic acid and 9 parts by weight of magnesium sulfate into the celery powder, controlling the temperature at 60 ℃, mechanically stirring at the rotating speed of 115rpm for 1.8 hours, washing with distilled water, carrying out reduced pressure filtration for 2 hours, and drying residues at room temperature to constant weight to obtain apigenin;
s2, weighing 30 parts by weight of glutaric anhydride, fully melting, sequentially adding 5 parts by weight of concentrated sulfuric acid and 8 parts by weight of the celery cellulose prepared in the step S1, and controlling the temperature to be 180 ℃ and uniformly stirring;
and S3, controlling the temperature to be 50 ℃ under the protection of nitrogen, sequentially adding 30 parts by weight of distilled water, 4 parts by weight of cerium nitrate and 5 parts by weight of propionamide, uniformly stirring, then adding 3 parts by weight of diisopropylethylamine and 4 parts by weight of diphenyl hypophosphoryl chloride, controlling the temperature to be 0 ℃ in an ice bath, reacting for 8 hours, and then heating to be 60 ℃ and reacting for 5 hours to obtain the grafted cellulose.
Example 3
The preparation of the grafted cellulose comprises the following steps:
s1, weighing 140 parts by weight of celery, crushing, sieving with a 100-mesh sieve, extracting the sieved celery with distilled water for 7.5 hours, washing, filtering, and drying after extraction is finished to obtain celery powder, sequentially adding 160 parts by weight of 3% hydrogen peroxide solution, 19 parts by weight of ethylenediamine tetraacetic acid and 10 parts by weight of magnesium sulfate into the celery powder, controlling the temperature at 60 ℃, mechanically stirring at the rotating speed of 125rpm for 1.8 hours, washing with distilled water, carrying out reduced pressure filtering for 2 hours, and drying residues at room temperature to constant weight to obtain celery cellulose;
s2, weighing 40 parts by weight of glutaric anhydride, fully melting, sequentially adding 8 parts by weight of concentrated sulfuric acid and 11 parts by weight of the celery cellulose prepared in the step S1, and controlling the temperature to be 190 ℃ and stirring uniformly;
and S3, controlling the temperature to be 50 ℃ under the protection of nitrogen, sequentially adding 40 parts by weight of distilled water, 6 parts by weight of cerium nitrate and 7 parts by weight of propionamide, uniformly stirring, then adding 4 parts by weight of diisopropylethylamine and 6 parts by weight of diphenyl hypophosphoryl chloride, controlling the temperature to be 0 ℃ in an ice bath, reacting for 9 hours, and then heating to be 65 ℃ and reacting for 5 hours to obtain the grafted cellulose.
Comparative example 1
Compared with example 3, glutaric anhydride in step S2 was 10 parts by weight, and the remaining steps and parameters were the same.
Comparative example 2
Compared with example 3, glutaric anhydride in step S2 was 50 parts by weight, and the remaining steps and parameters were the same.
Comparative example 3
Compared with example 3, the amount of propionamide in step S3 is 2 parts by weight, and the rest steps and parameters are the same.
Comparative example 4
Compared with example 3, the propionamide in step S3 is 8 parts by weight, and the rest steps and parameters are the same.
Comparative example 5
In comparison with example 3, diphenylphosphinic chloride in step S3 was 1 part by weight, and the rest of the steps and parameters were the same.
Comparative example 6
In comparison with example 3, diphenyl phosphoryl chloride in step S3 was 7 parts by weight, and the remaining steps and parameters were the same.
Example 4
The preparation method of the degradable flame-retardant plastic profile comprises the following steps:
adding deionized water into polyvinyl alcohol in the formula until the polyvinyl alcohol is completely dissolved, controlling the temperature to be 82 ℃, stirring for 1.5h, adding wheat starch, glycerol, urea and glycerol in the formula, gelatinizing for 1.5h, ultrasonically oscillating for 0.65h, adding grafted cellulose in the formula of the embodiment 3, continuously and mechanically stirring to obtain a plastic raw material solution, placing the plastic raw material solution in a mixer, controlling the temperature to be 117 ℃, mixing for 8min, taking out the mixed material, placing the mixed material in an extruder, carrying out extrusion molding, carrying out vacuum negative pressure cooling molding, carrying out uniform traction on the molded section by a tractor, and cutting the molded section at a fixed length by a cutting machine to obtain the degradable flame-retardant plastic section.
Example 5
The preparation method of the degradable flame-retardant plastic profile comprises the following steps:
adding deionized water into polyvinyl alcohol in the formula until the polyvinyl alcohol is completely dissolved, controlling the temperature to be 89 ℃, stirring for 1.5h, adding wheat starch, glycerol, urea and glycerol in the formula, gelatinizing for 1.5h, ultrasonically oscillating for 0.65h, adding grafted cellulose in the formula of the embodiment 3, continuously and mechanically stirring to obtain a plastic raw material solution, placing the plastic raw material solution in a mixer, controlling the temperature to be 120 ℃, mixing for 10min, taking out the mixed material, placing the mixed material in an extruder, carrying out extrusion molding, carrying out vacuum negative pressure cooling molding, carrying out uniform traction on the molded section by a tractor, and carrying out fixed-length cutting by a cutting machine to obtain the degradable flame-retardant plastic section.
Example 6
The preparation method of the degradable flame-retardant plastic profile comprises the following steps:
adding deionized water into polyvinyl alcohol in the formula until the polyvinyl alcohol is completely dissolved, controlling the temperature to be 89 ℃, stirring for 1.5h, adding wheat starch, glycerol, urea and glycerol in the formula, gelatinizing for 1.5h, ultrasonically oscillating for 0.65h, adding the grafted cellulose in the formula in the embodiment 3, continuously and mechanically stirring to obtain a plastic raw material solution, placing the plastic raw material solution in a mixer, controlling the temperature to be 123 ℃, mixing for 12min, taking out the mixed material, placing the mixed material in an extruder, performing extrusion molding, performing vacuum negative pressure cooling molding, drawing the molded section at a constant speed by a drawing machine, and cutting the molded section at a fixed length by a cutting machine to obtain the degradable flame-retardant plastic section.
Comparative example 7
In comparison with example 6, the grafted cellulose prepared in comparative example 1 was added and the remaining preparation method was identical to example 5.
Comparative example 8
In comparison with example 6, the grafted cellulose prepared in comparative example 2 was added and the rest of the preparation process was identical to example 5.
Comparative example 9
In comparison with example 6, the grafted cellulose prepared in comparative example 3 was added and the remaining preparation method was identical to example 5.
Comparative example 10
In comparison with example 6, the grafted cellulose prepared in comparative example 4 was added and the rest of the preparation process was identical to example 5.
Comparative example 11
In comparison with example 6, the grafted cellulose prepared in comparative example 5 was added and the remaining preparation method was identical to example 5.
Comparative example 12
In comparison with example 6, the grafted cellulose prepared in comparative example 6 was added and the remaining preparation method was identical to example 5.
Comparative example 13
In comparison with example 6, no glycerol was added and the remaining steps and parameters were identical.
Comparative example 14
In comparison with example 6, no glycerol was added and the remaining steps and parameters were identical.
Performance detection
(1) The plastic profiles obtained in examples 4-6 and comparative examples 7-12 were tested for flame retardancy according to GB/T5455-1997 using a fabric flame retardancy tester, model YG (B) 815D-I, the results of which are shown in Table 1.
(2) The plastic profiles obtained in examples 4-6 and comparative examples 7-12 were tested for limiting oxygen index according to GB/T5455-1997 using an apparatus type ASTM D6413-08, the results of which are shown in Table 1.
(3) The degradation performance of the composite material is tested by adopting a traditional soil burying method, and the section prepared by each experiment is buried in soil for testing in a natural environment, wherein the specific experimental operations are as follows:
1) Preparing the composite material into tensile property sample bars, selecting four sample bars for each sample, placing the sample bars into a vacuum constant-temperature drying oven, drying the sample bars for 12 hours at the temperature of 60 ℃, removing water, weighing and recording the mass of all the samples on an analytical balance.
2) The samples to be tested were encased in plastic mesh bags, and the same depth of embedment and sample spacing were maintained, with water alternating every two days.
3) Taking two weeks as a period from the time of burying, carefully washing the taken out sample with distilled water, washing to remove water at room temperature, drying at 60 deg.C in a drying oven for 12 times, weighing and recording all the taken out samples on an analytical balance, and accurately weighing the mass W t The weight loss ratios of the different patterns were calculated using the following formula.
In the formula: w 0 : sample quality before biodegradation performance test;
W t : quality of the sample after biodegradation performance test.
The plastic profiles obtained in examples 4 to 6 and comparative examples 13 to 14 were tested for their degradation properties, and the results are shown in Table 2.
(4) The tensile strength of the plastic profiles obtained in examples 4 to 6 and comparative examples 13 to 14 was measured by cutting the profiles into strips of 150 mm. Times.15 mm according to GB/T1040.3 to 2006, drying at 50 ℃ for 4 hours at a drawing speed of 200mm/min and measuring 3 specimens per group, taking the average value, and the results are shown in Table 2.
TABLE 1
| After flame time(s) | Charring length (mm) | Limiting oxygen index (%) | |
| Example 4 | 0 | 55 | 45.7 |
| Example 5 | 0 | 58 | 47.1 |
| Example 6 | 0 | 62 | 49.5 |
| Comparative example 7 | 3 | 43 | 33.6 |
| Comparative example 8 | 4 | 45 | 34.8 |
| Comparative example 9 | 3 | 47 | 35.2 |
| Comparative example 10 | 3 | 45 | 34.9 |
| Comparative example 11 | 4 | 45 | 33.7 |
| Comparative example 12 | 3 | 48 | 34.2 |
TABLE 2
As shown in Table 1, the plastic section prepared by the invention has excellent flame retardant property, the glutaric anhydride is added to destroy the hydrogen bond structure of the celery fiber, the length of a cellulose chain is increased, and the interface bonding strength of the celery fiber and other atoms is further improved; and the propionamide is introduced to be matched with cerium ions to react with diphenylphosphinic chloride, so that N and P elements are successfully grafted on the surface of the celery fiber, the fiber releases substances such as metaphosphoric acid, polyphosphoric acid and the like when being heated and decomposed, and the fiber is catalyzed to dehydrate into carbon, and the heat diffusion on the surface of the fiber is further blocked, so that the flame-retardant or combustion-slowing effect is achieved.
As shown in Table 2, the plastic profile prepared by the invention has outstanding degradation speed and tensile strength, glycerol and glycerol are added, the glycerol destroys most of lattice structures of wheat starch, so that cross-linking occurs between the wheat starch and cellulose chains, and since the wheat starch is easy to degrade per se, a hole structure is formed in the cross-linking process with the cellulose chains, a carbon source is provided for the growth of microorganisms in soil, the microorganisms absorb part of glycerol acting on the wheat starch, and the growth of the microorganisms per se is accelerated by the micromolecular glycerol, so that the degradation speed of the plastic profile is accelerated; the glycerol can penetrate into the wheat starch molecules to react with the hydroxyl in the wheat starch, so that the distance between the wheat starch molecules is increased, and the urea is used as a cross-linking agent, so that the cross-linking degree of the wheat starch, the polyvinyl alcohol and the glycerol is improved, and the relative sliding among the molecules under the action of external force is limited, so that the tensile strength of the profile is increased.
While one embodiment of the present invention has been described in detail, the description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (10)
1. The degradable flame-retardant plastic profile is characterized by comprising the following raw materials in percentage by weight:
2. the degradable flame-retardant plastic profile according to claim 1, wherein the preparation method of the degradable flame-retardant plastic profile comprises the following steps: adding deionized water into polyvinyl alcohol until the polyvinyl alcohol is completely dissolved, stirring at a controlled temperature, adding wheat starch, glycerol, urea and glycerol for gelatinization, ultrasonically oscillating, adding grafted cellulose, continuously and mechanically stirring to obtain a plastic raw material solution, controlling the temperature of the plastic raw material solution to be 117-123 ℃, mixing for 8-12min, taking out a mixed material, extruding and molding, cooling and molding at a vacuum negative pressure, uniformly drawing the molded section by a tractor, and cutting at a fixed length by a cutting machine to obtain the degradable flame-retardant plastic section.
3. The degradable flame-retardant plastic profile according to claim 2, wherein the stirring temperature is 82-95 ℃, the stirring time is 1-1.5h, the gelatinization time is 1.5-2h, the ultrasonic oscillation time is 0.5-0.8h, and the sealing and drying temperature and time are 20-25 ℃ and 46-50h respectively.
4. The degradable flame-retardant plastic profile according to claim 1, wherein the grafted cellulose is prepared by the following method:
s1, weighing celery, crushing and sieving the celery, extracting the sieved celery with distilled water for 7-8 hours, washing, filtering and drying the celery after extraction is finished to obtain celery powder, sequentially adding a 3% hydrogen peroxide solution, ethylenediamine tetraacetic acid and magnesium sulfate into the celery powder, mechanically stirring at a controlled temperature, washing with distilled water, carrying out reduced pressure filtration for 1-2 hours, and drying residues at room temperature to constant weight to obtain celery cellulose;
s2, weighing glutaric anhydride, fully melting, sequentially adding a catalyst and the celery cellulose prepared in the step S1, and uniformly stirring at controlled temperature;
and S3, controlling the temperature to be 45-50 ℃ under the protection of nitrogen, sequentially adding distilled water, cerium nitrate and propionamide, uniformly stirring, then adding an acid-binding agent and diphenyl hypophosphoryl chloride, controlling the temperature in an ice bath for reaction, and then heating for reaction to obtain the grafted cellulose.
5. The degradable flame-retardant plastic profile according to claim 4, wherein the ratio of celery to 3% hydrogen peroxide solution to ethylenediamine tetraacetic acid to magnesium sulfate in the step S1 is 100-140 parts by weight: 120-160:15-19:8-10.
6. The degradable flame-retardant plastic profile according to claim 4, wherein the sieving specification in the step S1 is 100 meshes, the speed is controlled to be 105-125rpm during mechanical stirring, the temperature is controlled to be 50-70 ℃, and the stirring time is 1.5-2h.
7. The degradable flame-retardant plastic profile according to claim 4, wherein the glutaric anhydride, the catalyst, the celery cellulose, the distilled water, the cerium nitrate, the propionamide, the acid binding agent and the diphenyl phosphoryl chloride in the steps S2 and S3 are added in an amount of 20-40 parts by weight: 2-8:5-11:20-40:2-6:3-7:2-4:2-6.
8. The degradable flame retardant plastic profile according to claim 4, wherein the stirring temperature in step S2 is 170-190 ℃.
9. The degradable flame-retardant plastic profile according to claim 4, wherein the temperature and time in the ice bath in step S3 are 0-1 ℃ and 7-9 hours respectively, and the temperature and time of the heating reaction are 55-65 ℃ and 5-6 hours respectively.
10. The degradable flame-retardant plastic profile according to claim 4, wherein the catalyst in step S2 is concentrated sulfuric acid, and the acid-binding agent in step S3 is diisopropylethylamine.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180094116A1 (en) * | 2016-09-30 | 2018-04-05 | Toyota Shatai Kabushiki Kaisha | Flame retardant resin composition and method for producing the same |
| CN110964297A (en) * | 2019-12-02 | 2020-04-07 | 安徽华赛包装有限公司 | Modification method of degradable plastic packaging material |
| CN111393717A (en) * | 2020-03-10 | 2020-07-10 | 宝兴精密(深圳)有限公司 | Degradable plastic and preparation method thereof |
| CN113480800A (en) * | 2021-05-31 | 2021-10-08 | 王川 | Biodegradable plastic and preparation method thereof |
| CN113845723A (en) * | 2021-09-29 | 2021-12-28 | 吕媛 | Biodegradable plastic and preparation method thereof |
| CN114507405A (en) * | 2021-09-02 | 2022-05-17 | 广东泰塑新材料科技有限公司 | Flame-retardant polyvinyl alcohol composite film and application thereof |
-
2022
- 2022-10-12 CN CN202211247014.4A patent/CN115449172A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180094116A1 (en) * | 2016-09-30 | 2018-04-05 | Toyota Shatai Kabushiki Kaisha | Flame retardant resin composition and method for producing the same |
| CN110964297A (en) * | 2019-12-02 | 2020-04-07 | 安徽华赛包装有限公司 | Modification method of degradable plastic packaging material |
| CN111393717A (en) * | 2020-03-10 | 2020-07-10 | 宝兴精密(深圳)有限公司 | Degradable plastic and preparation method thereof |
| CN113480800A (en) * | 2021-05-31 | 2021-10-08 | 王川 | Biodegradable plastic and preparation method thereof |
| CN114507405A (en) * | 2021-09-02 | 2022-05-17 | 广东泰塑新材料科技有限公司 | Flame-retardant polyvinyl alcohol composite film and application thereof |
| CN113845723A (en) * | 2021-09-29 | 2021-12-28 | 吕媛 | Biodegradable plastic and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 丁辰: "表面接枝方法阻燃改性Lyocell纤维的研究" * |
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