CN116948344B - Starch-based degradable polypropylene composite material and preparation method and application thereof - Google Patents
Starch-based degradable polypropylene composite material and preparation method and application thereof Download PDFInfo
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- CN116948344B CN116948344B CN202311220827.9A CN202311220827A CN116948344B CN 116948344 B CN116948344 B CN 116948344B CN 202311220827 A CN202311220827 A CN 202311220827A CN 116948344 B CN116948344 B CN 116948344B
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- 229920002472 Starch Polymers 0.000 title claims abstract description 174
- 235000019698 starch Nutrition 0.000 title claims abstract description 174
- 239000008107 starch Substances 0.000 title claims abstract description 174
- -1 polypropylene Polymers 0.000 title claims abstract description 141
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 140
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 158
- 239000010902 straw Substances 0.000 claims abstract description 158
- 238000002156 mixing Methods 0.000 claims abstract description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 32
- QHJWOSHIGFDANE-UHFFFAOYSA-N prop-2-enylphosphane Chemical compound PCC=C QHJWOSHIGFDANE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000007033 dehydrochlorination reaction Methods 0.000 claims abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- 238000007731 hot pressing Methods 0.000 claims abstract description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 33
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 241000209140 Triticum Species 0.000 claims description 11
- 235000021307 Triticum Nutrition 0.000 claims description 11
- MRRXLWNSVYPSRB-UHFFFAOYSA-N ethenyl-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)C=C MRRXLWNSVYPSRB-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007723 die pressing method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 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 abstract description 8
- 239000003063 flame retardant Substances 0.000 abstract description 8
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010411 cooking Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- 229910002651 NO3 Inorganic materials 0.000 description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920000388 Polyphosphate Polymers 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001205 polyphosphate Substances 0.000 description 7
- 235000011176 polyphosphates Nutrition 0.000 description 7
- 239000000835 fiber Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- 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)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a starch-based degradable polypropylene composite material, a preparation method and application thereof, and relates to the technical field of high polymer materials. When the starch-based degradable polypropylene composite material is prepared, soluble starch, an organosilicon monomer and propylene are initiated and polymerized into starch-based polypropylene through ammonium cerium nitrate; the method comprises the steps of (1) cooking crop straw powder through a sodium hydroxide solution to obtain pretreated straw powder, reacting the pretreated straw powder with allylphosphine dichloride to obtain pre-modified straw powder, and carrying out dehydrochlorination polycondensation reaction on the surface of the pre-modified straw powder to obtain modified straw powder; mixing and hot pressing starch-based polypropylene, modified straw powder and chloroplatinic acid to obtain the starch-based degradable polypropylene composite material. The starch-based degradable polypropylene composite material prepared by the invention has excellent flame retardant property, degradability and tensile strength.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a starch-based degradable polypropylene composite material, a preparation method and application thereof.
Background
Polypropylene is one of the most widely used general plastics at present, is solid at normal temperature, has no special smell, can resist acid-base corrosion, can bear higher temperature, has small density, high specific strength and excellent use performance, is widely used in actual life, such as bag making in supermarket, storage boxes in daily life, various shells and the like, and is also used as agricultural mulching film. However, polypropylene is very flammable, and the combustion process is accompanied by release of a large amount of heat and smoke, thereby bringing about fire hazards. Meanwhile, the preparation of raw materials consumes petroleum, is difficult to completely degrade and is easy to cause pollution.
In recent years, with the rapid development of technologies such as automobiles and electronics in China, the consumption of polypropylene increases year by year, and when accidents occur, the polypropylene is easy to cause strong fire, and meanwhile, the waste, damage and discarding of the products also cause huge environmental protection pressure. Therefore, in order to save petroleum resources, reduce environmental pressure and potential safety hazard, the polypropylene needs to be physically and chemically modified, and the flame retardance of the polypropylene is improved, so that the polypropylene is easy to degrade.
Disclosure of Invention
The invention aims to provide a starch-based degradable polypropylene composite material, and a preparation method and application thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a starch-based degradable polypropylene composite material is prepared by mixing and hot pressing starch-based polypropylene and modified straw powder.
Preferably, the starch-based polypropylene is polymerized from soluble starch, an organosilicon monomer and propylene.
Preferably, the organosilicon monomer is prepared by reacting D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane.
As optimization, the modified straw powder is prepared by preparing pretreated straw powder from crop straw powder through sodium hydroxide solution digestion, preparing the pretreated straw powder by reacting the pretreated straw powder with allyl phosphine dichloride, and performing dehydrochlorination polycondensation reaction on the surface of the pretreated straw powder by 4, 4-dihydroxybiphenyl and allyl phosphine dichloride.
The preparation method of the starch-based degradable polypropylene composite material comprises the following preparation steps:
(1) In a nitrogen atmosphere, soluble starch, an organic silicon monomer, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 1: (0.3 to 0.5): (40-50): (40-50): (40-50) uniformly mixing, adding the mixture into a high-pressure reaction kettle, enabling the addition amount to reach 60-70% of the capacity of the reaction kettle, stirring for 10-15 min at 10-20 ℃ at 200-300 r/min, adjusting the pH value to 4-6 by using hydrochloric acid solution with the mass fraction of 10%, heating to 30-70 ℃, introducing propylene to enable the pressure to reach 0.5-0.7 MPa, continuously introducing the mixture in the reaction process to enable the pressure to be kept unchanged until the mass of the introduced propylene is 3 times of the mass of the soluble starch, stopping introducing the mixture, and enabling cerium ammonium nitrate and pure water with the mass of 0.03-0.05 times of the mass of the soluble starch to be mixed according to the mass ratio of 1: uniformly mixing (40-60) to prepare an ammonium cerium nitrate solution, adding the ammonium cerium nitrate solution at a constant speed within 10-15 min, reacting for 0.5-3 h, opening a reaction kettle, placing at 40-50 ℃, drying at 100-500 Pa until no liquid exists, and washing 3-5 times by using acetone and absolute ethyl alcohol to prepare starch-based polypropylene;
(2) Soaking crop straw powder in pure water, standing for 10-12 hours at 20-30 ℃, then placing in a sodium hydroxide solution with mass fraction of 5%, steaming for 2-3 hours at 90-100 ℃, filtering, washing to be neutral by using the pure water, and drying for 8-10 hours at 60-70 ℃ to obtain pretreated straw powder; the pretreatment straw powder and allyl phosphine dichloride are mixed according to the mass ratio of 1: (2-3) uniformly mixing, adding anhydrous aluminum chloride with the mass of 0.003-0.004 times of that of the pretreated straw powder, stirring and reacting for 50-60 min at the temperature of 60-70 ℃ and the speed of 200-300 r/min in a nitrogen atmosphere, filtering, washing for 3-5 times by pure water, and drying for 8-10 h at the temperature of 60-70 ℃ to obtain the pre-modified straw powder; the preparation method comprises the following steps of (1) mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to a mass ratio of 1: (3-4): (0.03-0.04), heating to 60-70 ℃ under stirring in a nitrogen atmosphere, dropwise adding allyl phosphine dichloride at a constant speed within 25-30 min, continuing to react for 30-40 min after the dropwise adding is finished, heating to 90-100 ℃ and continuing to stir for 50-60 min, heating to 150-160 ℃ and continuing to stir for 20-30 min, filtering while the mixture is hot, cooling to room temperature, washing with absolute ethyl alcohol and toluene for 3-5 times, and drying at 60-70 ℃ for 8-10 h to obtain modified straw powder;
(3) And weighing starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 10% -50% of the total mass, the balance is starch-based polypropylene, and chloroplatinic acid with the mass of 0.003% -0.004 times of that of the starch-based polypropylene is added, and the starch-based polypropylene and the modified straw powder are placed in a three-dimensional linkage mixer to be uniformly mixed, and then poured into a mould for moulding, so that the starch-based degradable polypropylene composite material is prepared.
As optimization, the preparation method of the organic silicon monomer in the step (1) comprises the following steps: D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane are mixed according to a molar ratio of 1:1, adding sulfuric acid with the mass fraction of 98% which is 0.06-0.08 times that of D4H cyclotetrasiloxane, stirring at the temperature of 40-50 ℃ and the speed of 200-300 r/min for reaction for 8-10 hours, adding sodium bicarbonate to adjust the pH value to 6.8-7.2, filtering to remove solids, and drying at the temperature of 110-120 ℃ and the speed of 50-100 Pa for 10-12 hours.
As optimization, the crop straw powder in the step (2) is wheat straw powder, 80 meshes, and is produced in the Lianyuangang city of Jiangsu province.
As an optimization, the compression molding method in the step (3) comprises the following steps: pouring the mixture into a die for die pressing, wherein the die pressing temperature is 180 ℃, the die pressing pressure is 8MPa, the die pressing time is 30-40 min, and the die is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature.
Compared with the prior art, the invention has the following beneficial effects: in the preparation of the starch-based degradable polypropylene composite material, crop straw powder is steamed by sodium hydroxide solution to obtain pretreated straw powder, the pretreated straw powder reacts with allylphosphine dichloride to obtain pre-modified straw powder, and 4, 4-dihydroxybiphenyl and allylphosphine dichloride react on the surface of the pre-modified straw powder in a dehydrochlorination polycondensation way to obtain modified straw powder; mixing and hot pressing starch-based polypropylene, modified straw powder and chloroplatinic acid to obtain the starch-based degradable polypropylene composite material.
Firstly, the preparation raw materials contain soluble starch and crop straw powder, are natural plant raw materials, and have good degradation effect; reacting D4H cyclotetrasiloxane with vinyl pentamethyldisiloxane to obtain an organosilicon monomer; the soluble starch, the organic silicon monomer and propylene are initiated and polymerized into starch-based polypropylene through ceric ammonium nitrate, the organic silicon monomer can generate silicon dioxide to resist flame at high temperature, so that the flame retardant property is improved, a large number of silicon-hydrogen bond branched chains are introduced into the starch-based polypropylene by the organic silicon monomer, and a cross-linked network structure is formed through the silicon-hydrogen addition reaction and the carbon-carbon double bonds on the modified straw powder, so that the tensile strength is improved.
Secondly, the crop straw powder is steamed by sodium hydroxide solution to prepare pretreated straw powder, the pretreated straw powder is reacted with allyl phosphine dichloride to prepare pre-modified straw powder, 4-dihydroxybiphenyl and allyl phosphine dichloride are subjected to dehydrochlorination polycondensation reaction on the surface of the pre-modified straw powder to prepare modified straw powder, and the crop straw powder is subjected to pretreatment to dissolve substances such as monosaccharide, polysaccharide and the like in the straw powder, so that the structure of the crop straw powder is destroyed, fiber bundles are separated, starch-based polypropylene enters between the fiber bundles, the starch-based polypropylene wraps the crop straw powder better, and more active sites are exposed at the same time, thereby facilitating subsequent modification; the 4, 4-dihydroxybiphenyl and allyl phosphine dichloride are subjected to dehydrochlorination and polycondensation on the surface of the pre-modified straw powder to generate a polyphosphate branched chain, and when the pre-modified straw powder is burnt, the polyphosphate branched chain is thermally decomposed to generate phosphoric acid, polyphosphoric acid and the like to promote crosslinking of the starch-based degradable polypropylene composite material to generate a compact carbon layer to cover the surface, so that the volatile combustible gas and air are blocked to exchange gas, heat transfer is inhibited, further thermal decomposition of the starch-based degradable polypropylene composite material is prevented, and the flame retardant property is improved; and the polyphosphate branched chain contains a large number of carbon-carbon double bonds, and can be subjected to silicon-hydrogen reaction crosslinking with silicon-hydrogen bonds on starch-based polypropylene, so that the tensile strength is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the present invention, a detailed description will now be given by way of the following examples.
Example 1
The preparation method of the starch-based degradable polypropylene composite material mainly comprises the following preparation steps:
(1) D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane are mixed according to a molar ratio of 1:1, uniformly mixing, adding sulfuric acid with the mass fraction of 98% which is 0.06 times that of D4H cyclotetrasiloxane, stirring at 40 ℃ and 200r/min for reaction for 10 hours, adding sodium bicarbonate to adjust the pH to 6.8, filtering to remove solids, and drying at 110 ℃ and 50Pa for 12 hours to obtain an organosilicon monomer; in a nitrogen atmosphere, soluble starch, an organic silicon monomer, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 1:0.3:40:40:40, uniformly mixing and adding the mixture into a high-pressure reaction kettle, enabling the addition amount to reach 60% of the capacity of the reaction kettle, stirring for 10min at 10 ℃ and 200r/min, adjusting the pH value to 5 by using hydrochloric acid solution with the mass fraction of 10%, heating to 40 ℃, introducing propylene to enable the pressure to reach 0.5MPa, continuously introducing the propylene in the reaction process to enable the pressure to be unchanged until the mass of the introduced propylene is 3 times of the mass of the soluble starch, stopping introducing the propylene, and enabling the mass of the cerium ammonium nitrate and pure water which are 0.03 times of the mass of the soluble starch to be 1 according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, uniformly adding the ceric ammonium nitrate solution in 10min, reacting for 1.5h, opening a reaction kettle, placing at 40 ℃, drying at 100Pa until no liquid exists, and washing with acetone and absolute ethyl alcohol for 5 times to prepare starch-based polypropylene;
(2) Soaking wheat straw powder in pure water, standing at 20 ℃ for 10 hours, placing in sodium hydroxide solution with mass fraction of 5%, steaming at 90 ℃ for 3 hours, filtering, washing with pure water to be neutral, and drying at 60 ℃ for 8 hours to obtain pretreated straw powder; the pretreatment straw powder and allyl phosphine dichloride are mixed according to the mass ratio of 1:2, uniformly mixing, adding anhydrous aluminum chloride with the mass of 0.003 times of that of the pretreated straw powder, stirring and reacting for 60 minutes at the temperature of 60 ℃ and the speed of 200r/min in a nitrogen atmosphere, filtering, washing for 3 times by pure water, and drying for 10 hours at the temperature of 60 ℃ to obtain the pre-modified straw powder; the preparation method comprises the following steps of (1) mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to a mass ratio of 1:3:0.03, heating to 70 ℃ under stirring at 200r/min in a nitrogen atmosphere, dropwise adding allyl phosphine dichloride at a constant speed within 25-30 min, continuing to react for 30min after the dropwise adding is finished, heating to 90 ℃ and continuing to stir for 50min, heating to 150 ℃ and continuing to stir for 30min, filtering while the mixture is hot, cooling to room temperature, washing with absolute ethyl alcohol and toluene for 3 times, and drying at 60 ℃ for 10h to obtain modified straw powder;
(3) And (3) weighing starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 30% of the total mass, the balance is starch-based polypropylene, chloroplatinic acid with the mass of 0.003 times of that of the starch-based polypropylene is added, the starch-based polypropylene and the modified straw powder are uniformly mixed in a three-dimensional linkage mixer, and then the mixture is poured into a mould for moulding, the moulding temperature is 180 ℃, the pressure is 8MPa, the time is 40min, and the mould is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature, so that the starch-based degradable polypropylene composite material is prepared.
Example 2
The preparation method of the starch-based degradable polypropylene composite material mainly comprises the following preparation steps:
(1) D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane are mixed according to a molar ratio of 1:1, adding sulfuric acid with the mass fraction of 98% which is 0.07 times that of D4H cyclotetrasiloxane, stirring at 45 ℃ and 250r/min for reaction for 9 hours, adding sodium bicarbonate to adjust the pH to 7, filtering to remove solids, and drying at 115 ℃ and 70Pa for 11 hours to obtain an organosilicon monomer; in a nitrogen atmosphere, soluble starch, an organic silicon monomer, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 1:0.4:45:45:45, uniformly mixing and adding the mixture into a high-pressure reaction kettle, enabling the adding amount to reach 65% of the capacity of the reaction kettle, stirring the mixture for 12min at 15 ℃ and 250r/min, adjusting the pH value to 5 by using hydrochloric acid solution with the mass fraction of 10%, heating the mixture to 40 ℃, introducing propylene to enable the pressure to reach 0.6MPa, continuously introducing the mixture in the reaction process to enable the pressure to be unchanged until the mass of the introduced propylene is 3 times of the mass of soluble starch, stopping introducing the mixture, and enabling cerium ammonium nitrate and pure water with the mass of 0.03 times of the mass of the soluble starch to be mixed according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, adding the ceric ammonium nitrate solution at a uniform speed within 12min, reacting for 1.5h, opening a reaction kettle, placing at 45 ℃, drying at 300Pa until no liquid exists, and washing with acetone and absolute ethyl alcohol for 4 times to prepare starch-based polypropylene;
(2) Soaking wheat straw powder in pure water, standing at 25 ℃ for 11 hours, placing in sodium hydroxide solution with mass fraction of 5%, steaming at 95 ℃ for 2.5 hours, filtering, washing with pure water to be neutral, and drying at 65 ℃ for 9 hours to obtain pretreated straw powder; the pretreatment straw powder and allyl phosphine dichloride are mixed according to the mass ratio of 1:2.5, uniformly mixing, adding anhydrous aluminum chloride with the mass of 0.0035 times of that of the pretreated straw powder, stirring and reacting for 55min at the temperature of 250r/min in a nitrogen atmosphere, filtering and washing for 4 times by pure water, and drying for 9h at the temperature of 65 ℃ to obtain the pre-modified straw powder; the preparation method comprises the following steps of (1) mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to a mass ratio of 1:3.5:0.035, heating to 65 ℃ under stirring at 250r/min in nitrogen atmosphere, dripping allyl phosphine dichloride at constant speed within 28min, continuing to react for 35min after dripping, heating to 95 ℃ and continuing to stir for 55min, heating to 155 ℃ and continuing to stir for 25min, filtering while hot, cooling to room temperature, washing with absolute ethyl alcohol and toluene for 4 times, and drying at 65 ℃ for 9h to obtain modified straw powder;
(3) And (3) weighing starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 30% of the total mass, the balance is starch-based polypropylene, chloroplatinic acid with the mass of 0.0035 times of that of the starch-based polypropylene is added, the starch-based polypropylene and the modified straw powder are uniformly mixed in a three-dimensional linkage mixer, and then the mixture is poured into a mould for moulding, the moulding temperature is 180 ℃, the pressure is 8MPa, the time is 35min, and the mould is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature, so that the starch-based degradable polypropylene composite material is prepared.
Example 3
The preparation method of the starch-based degradable polypropylene composite material mainly comprises the following preparation steps:
(1) D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane are mixed according to a molar ratio of 1:1, adding sulfuric acid with the mass fraction of 98% which is 0.08 times that of D4H cyclotetrasiloxane, stirring at 50 ℃ and 300r/min for reaction for 8 hours, adding sodium bicarbonate to adjust the pH to 7.2, filtering to remove solids, and drying at 120 ℃ and 100Pa for 10 hours to prepare an organosilicon monomer; in a nitrogen atmosphere, soluble starch, an organic silicon monomer, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 1:0.5:50:50:50, uniformly mixing and adding the mixture into a high-pressure reaction kettle, enabling the addition amount to reach 70% of the capacity of the reaction kettle, stirring for 10min at 20 ℃ and 300r/min, adjusting the pH value to 5 by using hydrochloric acid solution with the mass fraction of 10%, heating to 40 ℃, introducing propylene to enable the pressure to reach 0.6MPa, continuously introducing the propylene in the reaction process to enable the pressure to be unchanged until the mass of the introduced propylene is 3 times of the mass of the soluble starch, stopping introducing the propylene, and enabling the mass of the cerium ammonium nitrate and pure water which are 0.03 times of the mass of the soluble starch to be 1 according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, adding the ceric ammonium nitrate solution at a uniform speed within 12min, reacting for 1.5h, opening a reaction kettle, placing at 50 ℃, drying at 500Pa until no liquid exists, and washing with acetone and absolute ethyl alcohol for 5 times to prepare starch-based polypropylene;
(2) Soaking wheat straw powder in pure water, standing at 30 ℃ for 10 hours, placing in sodium hydroxide solution with mass fraction of 5%, steaming at 100 ℃ for 2 hours, filtering, washing with pure water to neutrality, and drying at 70 ℃ for 8 hours to obtain pretreated straw powder; the pretreatment straw powder and allyl phosphine dichloride are mixed according to the mass ratio of 1:3, uniformly mixing, adding anhydrous aluminum chloride with the mass of 0.004 times of that of the pretreated straw powder, stirring and reacting for 50min at 70 ℃ and 300r/min in a nitrogen atmosphere, filtering and washing for 5 times by pure water, and drying for 8h at 70 ℃ to obtain the pre-modified straw powder; the preparation method comprises the following steps of (1) mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to a mass ratio of 1:4:0.04, heating to 70 ℃ under stirring at 300r/min in nitrogen atmosphere, dropwise adding allyl phosphine dichloride at a constant speed within 30min, continuing to react for 40min after the dropwise adding is finished, heating to 100 ℃ and continuing to stir for 60min, heating to 160 ℃ and continuing to stir for 20min, filtering while hot, cooling to room temperature, washing with absolute ethyl alcohol and toluene for 5 times, and drying at 70 ℃ for 8h to obtain modified straw powder;
(3) And (3) weighing starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 30% of the total mass, the balance is starch-based polypropylene, chloroplatinic acid with the mass of 0.004 times of that of the starch-based polypropylene is added, the starch-based polypropylene and the modified straw powder are uniformly mixed in a three-dimensional linkage mixer, and then the mixture is poured into a mould for moulding, the moulding temperature is 180 ℃, the pressure is 8MPa, the time is 35min, and the mould is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature, so that the starch-based degradable polypropylene composite material is prepared.
Comparative example 1
The difference from example 2 is only that in step (1), the "pH was adjusted to 5 with a 10% by mass hydrochloric acid solution" was adjusted to 2 with a 10% by mass hydrochloric acid solution ".
Comparative example 2
The difference from example 2 is only that in step (1), the "pH was adjusted to 5 with a 10% by mass hydrochloric acid solution" was adjusted to 3 with a 10% by mass hydrochloric acid solution ".
Comparative example 3
The difference from example 2 is only that in step (1), the "pH was adjusted to 5 with a 10% by mass hydrochloric acid solution" was adjusted to 4 with a 10% by mass hydrochloric acid solution ".
Comparative example 4
The difference from example 2 is only that in step (1), the "pH was adjusted to 5 with a 10% by mass hydrochloric acid solution" was adjusted to 6 with a 10% by mass hydrochloric acid solution ".
Comparative example 5
The difference from example 2 is only that in step (1), the "pH was adjusted to 5 with a 10% by mass hydrochloric acid solution" was adjusted to 7 with a 10% by mass hydrochloric acid solution ".
Comparative example 6
The difference from example 2 is only that in step (1), the "pH was adjusted to 5 with a 10% by mass hydrochloric acid solution" was adjusted to 8 with a 10% by mass hydrochloric acid solution ".
Comparative example 7
The difference from example 2 is only that in step (1), the pH value in step (1) is adjusted to 5 by using hydrochloric acid solution with mass fraction of 10%, the temperature is raised to 40 ℃, propylene is introduced to make the pressure reach 0.6MPa, the introduction is continued in the reaction process to keep the pressure unchanged until the mass of the introduced propylene is 3 times that of the soluble starch, and the introduction is stopped, and cerium ammonium nitrate with mass of 0.03 times that of the soluble starch and pure water are mixed according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, uniformly adding the ceric ammonium nitrate solution in 12min, reacting for 1.5h, opening the reaction kettle, placing at 45 ℃, drying at 300Pa until no liquid exists, washing with acetone and absolute ethyl alcohol for 4 times, and obtaining starch-based polypropylene, wherein the temperature is increased to 40 ℃ and is adjusted to be increased to 30 ℃.
Comparative example 8
The difference from example 2 is only that in step (1), the temperature was "raised to 40 ℃ and" adjusted to "raised to 50 ℃.
Comparative example 9
The difference from example 2 is only that in step (1), the temperature was "raised to 40 ℃ and" adjusted to "raised to 60 ℃.
Comparative example 10
The difference from example 2 is only that in step (1), the temperature was "raised to 40 ℃ and" adjusted to "raised to 70 ℃.
Comparative example 11
The difference from example 2 is only that in step (1), the "cerium ammonium nitrate and pure water in an amount of 0.03 times the mass of the soluble starch are mixed in a mass ratio of 1:50, uniformly mixing to prepare ammonium ceric nitrate solution, wherein the ammonium ceric nitrate solution is prepared by' adjusting ammonium ceric nitrate and pure water which are 0.01 times of soluble starch in mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution.
Comparative example 12
The difference from example 2 is only that in step (1), the "cerium ammonium nitrate and pure water in an amount of 0.03 times the mass of the soluble starch are mixed in a mass ratio of 1:50, uniformly mixing to prepare ammonium ceric nitrate solution, wherein the ammonium ceric nitrate solution is prepared by' adjusting ammonium ceric nitrate and pure water which are 0.02 times of the mass of soluble starch according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution.
Comparative example 13
The difference from example 2 is only that in step (1), the "cerium ammonium nitrate and pure water in an amount of 0.03 times the mass of the soluble starch are mixed in a mass ratio of 1:50, uniformly mixing to prepare ammonium ceric nitrate solution, wherein the ammonium ceric nitrate solution is prepared by' adjusting ammonium ceric nitrate and pure water which are 0.04 times of soluble starch in mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution.
Comparative example 14
The difference from example 2 is only that in step (1), the "cerium ammonium nitrate and pure water in an amount of 0.03 times the mass of the soluble starch are mixed in a mass ratio of 1:50, uniformly mixing to prepare ammonium ceric nitrate solution, wherein the ammonium ceric nitrate solution is prepared by' adjusting ammonium ceric nitrate and pure water which are 0.05 times of the mass of soluble starch according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution.
Comparative example 15
The difference from example 2 is only that in step (1), the "cerium ammonium nitrate solution was added at a constant speed within 12min in step (1), reacted for 1.5 hours, the reaction vessel was opened and placed at 45 ℃, dried at 300Pa until no liquid was present, and washed with acetone and absolute ethanol for 4 times, to prepare starch-based polypropylene", wherein the "reaction for 1.5 hours" was adjusted to "reaction for 0.5 hours".
Comparative example 16
The difference from example 2 is only that in the step (1), the "reaction 1.5h" was adjusted to the "reaction 1h".
Comparative example 17
The difference from example 2 is only that in step (1), the "reaction 1.5h" was adjusted to "reaction 2h".
Comparative example 18
The difference from example 2 is only that in step (1), the "reaction 1.5h" was adjusted to the "reaction 2.5h".
Comparative example 19
The difference from example 2 is only that in step (1), the "reaction 1.5h" was adjusted to "reaction 3h".
Comparative example 20
The difference from example 2 is only that in step (3), "starch-based polypropylene and modified straw powder are weighed, wherein the addition amount of the modified straw powder is 30% of the total mass, and the balance is starch-based polypropylene is" adjusted to "starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 10% of the total mass, and the balance is starch-based polypropylene".
Comparative example 21
The difference from example 2 is only that in step (3), "starch-based polypropylene and modified straw powder are weighed, wherein the addition amount of the modified straw powder is 30% of the total mass, and the balance is starch-based polypropylene is" adjusted to "starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 20% of the total mass, and the balance is starch-based polypropylene".
Comparative example 22
The difference from example 2 is only that in step (3), "starch-based polypropylene and modified straw powder are weighed, wherein the addition amount of the modified straw powder is 30% of the total mass, and the balance is starch-based polypropylene is" adjusted to "starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 40% of the total mass, and the balance is starch-based polypropylene".
Comparative example 23
The difference from example 2 is only that in step (3), "starch-based polypropylene and modified straw powder are weighed, wherein the addition amount of the modified straw powder is 30% of the total mass, and the balance is starch-based polypropylene is" adjusted to "starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 50% of the total mass, and the balance is starch-based polypropylene".
Comparative example 24
The preparation method of the starch-based degradable polypropylene composite material mainly comprises the following preparation steps:
(1) D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane are mixed according to a molar ratio of 1:1, adding sulfuric acid with the mass fraction of 98% which is 0.07 times that of D4H cyclotetrasiloxane, stirring at 45 ℃ and 250r/min for reaction for 9 hours, adding sodium bicarbonate to adjust the pH to 7, filtering to remove solids, and drying at 115 ℃ and 70Pa for 11 hours to obtain an organosilicon monomer; in a nitrogen atmosphere, organosilicon monomer, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 0.4:45:45:45, uniformly mixing and adding the mixture into a high-pressure reaction kettle, enabling the adding amount to reach 65% of the capacity of the reaction kettle, stirring the mixture for 12min at 15 ℃ and 250r/min, adjusting the pH value to 5 by using hydrochloric acid solution with the mass fraction of 10%, heating the mixture to 40 ℃, introducing propylene to enable the pressure to reach 0.6MPa, continuously introducing the mixture in the reaction process to enable the pressure to be unchanged until the mass of the introduced propylene is 3 times of the mass of the organosilicon monomer, stopping introducing the mixture, and enabling cerium ammonium nitrate and pure water with the mass of 0.03 times of the mass of the organosilicon monomer to be mixed according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, adding the ceric ammonium nitrate solution at a uniform speed within 12min, reacting for 1.5h, opening a reaction kettle, placing at 45 ℃, drying at 300Pa until no liquid exists, and washing for 4 times by using acetone and absolute ethyl alcohol to prepare the organosilicon-based polypropylene;
(2) Soaking wheat straw powder in pure water, standing at 25 ℃ for 11 hours, placing in sodium hydroxide solution with mass fraction of 5%, steaming at 95 ℃ for 2.5 hours, filtering, washing with pure water to be neutral, and drying at 65 ℃ for 9 hours to obtain pretreated straw powder; the pretreatment straw powder and allyl phosphine dichloride are mixed according to the mass ratio of 1:2.5, uniformly mixing, adding anhydrous aluminum chloride with the mass of 0.0035 times of that of the pretreated straw powder, stirring and reacting for 55min at the temperature of 250r/min in a nitrogen atmosphere, filtering and washing for 4 times by pure water, and drying for 9h at the temperature of 65 ℃ to obtain the pre-modified straw powder; the preparation method comprises the following steps of (1) mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to a mass ratio of 1:3.5:0.035, heating to 65 ℃ under stirring at 250r/min in nitrogen atmosphere, dripping allyl phosphine dichloride at constant speed within 28min, continuing to react for 35min after dripping, heating to 95 ℃ and continuing to stir for 55min, heating to 155 ℃ and continuing to stir for 25min, filtering while hot, cooling to room temperature, washing with absolute ethyl alcohol and toluene for 4 times, and drying at 65 ℃ for 9h to obtain modified straw powder;
(3) And (3) weighing the organosilicon-based polypropylene and the modified straw powder, wherein the addition amount of the modified straw powder is 30% of the total mass, the balance is the organosilicon-based polypropylene, then chloroplatinic acid with the mass of 0.0035 times that of the organosilicon-based polypropylene is added, the mixture is placed into a three-dimensional linkage mixer to be uniformly mixed, and then the mixture is poured into a mould to be molded, the molding temperature is 180 ℃, the pressure is 8MPa, the time is 35min, the pressure is kept unchanged, natural cooling is carried out to room temperature, and then the mould is opened, and the organosilicon-based polypropylene degradable polypropylene composite material is obtained.
Comparative example 25
The preparation method of the starch-based degradable polypropylene composite material mainly comprises the following preparation steps:
(1) Soluble starch, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 1:45:45:45, uniformly mixing and adding the mixture into a high-pressure reaction kettle, enabling the adding amount to reach 65% of the capacity of the reaction kettle, stirring the mixture for 12min at 15 ℃ and 250r/min, adjusting the pH value to 5 by using hydrochloric acid solution with the mass fraction of 10%, heating the mixture to 40 ℃, introducing propylene to enable the pressure to reach 0.6MPa, continuously introducing the mixture in the reaction process to enable the pressure to be unchanged until the mass of the introduced propylene is 3 times of the mass of soluble starch, stopping introducing the mixture, and enabling cerium ammonium nitrate and pure water with the mass of 0.03 times of the mass of the soluble starch to be mixed according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, adding the ceric ammonium nitrate solution at a uniform speed within 12min, reacting for 1.5h, opening a reaction kettle, placing at 45 ℃, drying at 300Pa until no liquid exists, and washing with acetone and absolute ethyl alcohol for 4 times to prepare starch-based polypropylene;
(2) Soaking wheat straw powder in pure water, standing at 25 ℃ for 11 hours, placing in sodium hydroxide solution with mass fraction of 5%, steaming at 95 ℃ for 2.5 hours, filtering, washing with pure water to be neutral, and drying at 65 ℃ for 9 hours to obtain pretreated straw powder; the pretreatment straw powder and allyl phosphine dichloride are mixed according to the mass ratio of 1:2.5, uniformly mixing, adding anhydrous aluminum chloride with the mass of 0.0035 times of that of the pretreated straw powder, stirring and reacting for 55min at the temperature of 250r/min in a nitrogen atmosphere, filtering and washing for 4 times by pure water, and drying for 9h at the temperature of 65 ℃ to obtain the pre-modified straw powder; the preparation method comprises the following steps of (1) mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to a mass ratio of 1:3.5:0.035, heating to 65 ℃ under stirring at 250r/min in nitrogen atmosphere, dripping allyl phosphine dichloride at constant speed within 28min, continuing to react for 35min after dripping, heating to 95 ℃ and continuing to stir for 55min, heating to 155 ℃ and continuing to stir for 25min, filtering while hot, cooling to room temperature, washing with absolute ethyl alcohol and toluene for 4 times, and drying at 65 ℃ for 9h to obtain modified straw powder;
(3) And (3) weighing starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 30% of the total mass, the balance is starch-based polypropylene, chloroplatinic acid with the mass of 0.0035 times of that of the starch-based polypropylene is added, the starch-based polypropylene and the modified straw powder are uniformly mixed in a three-dimensional linkage mixer, and then the mixture is poured into a mould for moulding, the moulding temperature is 180 ℃, the pressure is 8MPa, the time is 35min, and the mould is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature, so that the starch-based degradable polypropylene composite material is prepared.
Comparative example 26
The preparation method of the starch-based degradable polypropylene composite material mainly comprises the following preparation steps:
(1) D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane are mixed according to a molar ratio of 1:1, adding sulfuric acid with the mass fraction of 98% which is 0.07 times that of D4H cyclotetrasiloxane, stirring at 45 ℃ and 250r/min for reaction for 9 hours, adding sodium bicarbonate to adjust the pH to 7, filtering to remove solids, and drying at 115 ℃ and 70Pa for 11 hours to obtain an organosilicon monomer; in a nitrogen atmosphere, soluble starch, an organic silicon monomer, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 1:0.4:45:45:45, uniformly mixing and adding the mixture into a high-pressure reaction kettle, enabling the adding amount to reach 65% of the capacity of the reaction kettle, stirring the mixture for 12min at 15 ℃ and 250r/min, adjusting the pH value to 5 by using hydrochloric acid solution with the mass fraction of 10%, heating the mixture to 40 ℃, introducing propylene to enable the pressure to reach 0.6MPa, continuously introducing the mixture in the reaction process to enable the pressure to be unchanged until the mass of the introduced propylene is 3 times of the mass of soluble starch, stopping introducing the mixture, and enabling cerium ammonium nitrate and pure water with the mass of 0.03 times of the mass of the soluble starch to be mixed according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, adding the ceric ammonium nitrate solution at a uniform speed within 12min, reacting for 1.5h, opening a reaction kettle, placing at 45 ℃, drying at 300Pa until no liquid exists, and washing with acetone and absolute ethyl alcohol for 4 times to prepare starch-based polypropylene;
(2) Wheat straw powder and allylphosphine dichloride are mixed according to the mass ratio of 1:2.5, uniformly mixing, adding anhydrous aluminum chloride with the mass of 0.0035 times that of the wheat straw powder, stirring and reacting for 55min at the temperature of 250r/min in a nitrogen atmosphere, filtering and washing for 4 times by pure water, and drying for 9h at the temperature of 65 ℃ to obtain pre-modified straw powder; the preparation method comprises the following steps of (1) mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to a mass ratio of 1:3.5:0.035, heating to 65 ℃ under stirring at 250r/min in nitrogen atmosphere, dripping allyl phosphine dichloride at constant speed within 28min, continuing to react for 35min after dripping, heating to 95 ℃ and continuing to stir for 55min, heating to 155 ℃ and continuing to stir for 25min, filtering while hot, cooling to room temperature, washing with absolute ethyl alcohol and toluene for 4 times, and drying at 65 ℃ for 9h to obtain modified straw powder;
(3) And (3) weighing starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 30% of the total mass, the balance is starch-based polypropylene, chloroplatinic acid with the mass of 0.0035 times of that of the starch-based polypropylene is added, the starch-based polypropylene and the modified straw powder are uniformly mixed in a three-dimensional linkage mixer, and then the mixture is poured into a mould for moulding, the moulding temperature is 180 ℃, the pressure is 8MPa, the time is 35min, and the mould is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature, so that the starch-based degradable polypropylene composite material is prepared.
Comparative example 27
The preparation method of the starch-based degradable polypropylene composite material mainly comprises the following preparation steps:
(1) D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane are mixed according to a molar ratio of 1:1, adding sulfuric acid with the mass fraction of 98% which is 0.07 times that of D4H cyclotetrasiloxane, stirring at 45 ℃ and 250r/min for reaction for 9 hours, adding sodium bicarbonate to adjust the pH to 7, filtering to remove solids, and drying at 115 ℃ and 70Pa for 11 hours to obtain an organosilicon monomer; in a nitrogen atmosphere, soluble starch, an organic silicon monomer, pure water, ethanol and tetrahydrofuran are mixed according to the mass ratio of 1:0.4:45:45:45, uniformly mixing and adding the mixture into a high-pressure reaction kettle, enabling the adding amount to reach 65% of the capacity of the reaction kettle, stirring the mixture for 12min at 15 ℃ and 250r/min, adjusting the pH value to 5 by using hydrochloric acid solution with the mass fraction of 10%, heating the mixture to 40 ℃, introducing propylene to enable the pressure to reach 0.6MPa, continuously introducing the mixture in the reaction process to enable the pressure to be unchanged until the mass of the introduced propylene is 3 times of the mass of soluble starch, stopping introducing the mixture, and enabling cerium ammonium nitrate and pure water with the mass of 0.03 times of the mass of the soluble starch to be mixed according to the mass ratio of 1:50, uniformly mixing to prepare ceric ammonium nitrate solution, adding the ceric ammonium nitrate solution at a uniform speed within 12min, reacting for 1.5h, opening a reaction kettle, placing at 45 ℃, drying at 300Pa until no liquid exists, and washing with acetone and absolute ethyl alcohol for 4 times to prepare starch-based polypropylene;
(2) Soaking wheat straw powder in pure water, standing at 25 ℃ for 11 hours, placing in sodium hydroxide solution with mass fraction of 5%, steaming at 95 ℃ for 2.5 hours, filtering, washing with pure water to be neutral, and drying at 65 ℃ for 9 hours to obtain pretreated straw powder;
(3) And (3) weighing starch-based polypropylene and pretreated straw powder, wherein the addition amount of the pretreated straw powder is 30% of the total mass, the balance is starch-based polypropylene, chloroplatinic acid with the mass of 0.0035 times of that of the starch-based polypropylene is added, the starch-based polypropylene and the pretreated straw powder are uniformly mixed in a three-dimensional linkage mixer, and then the mixture is poured into a mould for moulding, the moulding temperature is 180 ℃, the pressure is 8MPa, the time is 35min, and the mould is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature, so that the starch-based degradable polypropylene composite material is prepared.
Test example 1
Determination of optimal conditions for starch-based Polypropylene (pH, reaction temperature, addition of cerium ammonium nitrate, reaction time)
The testing method comprises the following steps: analysis was performed by grafting, using conventional Soxhlet extraction. Due to the presence of starch-based polypropylene and starch-free polymer, as well as a portion of unreacted propylene monomer, in the product after the reaction has ended. Therefore, for determining the grafting ratio, it is necessary to remove the monomers from the starch-free polymer. After the reaction is finished, the product is placed in a Soxhlet extractor, and the starch-based polypropylene is not easily dissolved in an organic solvent because the product does not contain starch polymer and monomer, and is extracted for 72 hours by adopting acetone, and pure starch-based polypropylene can be obtained after vacuum drying, and the results are shown in Table 1.
Grafting ratio: g (%) = [ (M) 1 -M 0 ）/M 0 ]*100%； M 0 Representing the feeding quality of the soluble starch; m is M 1 Representing the mass of starch-based polypropylene after soxhlet extraction.
As can be seen from the comparison of example 2 and comparative examples 1 to 6, the grafting ratio of starch is higher under acidic conditions. Under the acidic condition, the oxidability of the ammonium ceric nitrate is stronger than that under the alkaline condition, and the cerium ions are easy to form hydroxide colloid precipitation under the alkaline condition, so that the oxidant is deactivated, less free radicals are generated, and the grafting rate under the alkaline condition is lower; under strongly acidic conditions, the soluble starch is partially hydrolyzed, resulting in a similar decrease in grafting, and therefore the grafting is highest at a pH of about 5.
As can be seen from the comparison of example 2 and comparative examples 7 to 10, the grafting ratio was highest when the reaction temperature was 40 ℃. At low temperature, the reaction rate of the initiator for oxidizing hydroxyl groups to generate active sites is slower, the temperature rise is favorable for generating free radicals, but propylene is easier to generate self-polymerization reaction to generate polypropylene, and the grafting rate of starch is influenced. The optimum reaction temperature was thus controlled to 40 ℃.
As can be seen from comparison of example 2 and comparative examples 11 to 14, the effect of the addition amount of ceric ammonium nitrate on the grafting rate is more remarkable, when the addition amount of ceric ammonium nitrate is small, the generated free radical is less, the grafting rate is lower, and since ceric ammonium nitrate can also cause propylene self-polymerization, when the concentration of ceric ammonium nitrate is large, the generated propylene homopolymer is more, the self-polymerization reaction and the copolymerization reaction of propylene are in competition, the grafting rate is also lower, and through experiments, the grafting rate is highest when the addition amount of ceric ammonium nitrate is 0.03 times of the addition amount of starch.
As can be seen from comparison of the examples 2 and the comparative examples 15 to 19, when the reaction time is 1.5 hours, the basic grafting ratio reaches the maximum, the subsequent reaction time is prolonged, the grafting ratio is not greatly improved, and from the viewpoint of experimental efficiency, the reaction time is controlled to be 1.5 hours.
Therefore, the reaction conditions of example 2 were selected as the optimal choice, wherein the pH was 5, the reaction temperature was 40℃and the amount of ceric ammonium nitrate was 0.03 times the mass of the starch added, and the reaction time was 1.5 hours.
Test example 2
Determination of optimal addition amount of modified straw powder
The testing method comprises the following steps: the tensile strength of the starch-based degradable polypropylene composite material is determined by mechanical properties, and the tensile speed is 2mm/min according to GB/T1040.1-2006; the bending strength and the bending modulus of the starch-based degradable polypropylene composite material are tested according to GB/T9341-2008, and the loading speed is 2mm/min; the impact strength of the starch-based degradable polypropylene composite material was tested according to GB/T10431-2008, and the results are shown in Table 2.
By comparing the embodiment 2 with the comparative examples 20-23, it can be found that the mechanical properties of the starch-based degradable polypropylene composite material are improved and reduced along with the increase of the modified straw powder, because the content of the plastic matrix is sufficient when the addition amount of the modified straw powder is small, and the modified straw powder can be well wrapped; when the modified straw powder is too much, the content of the plastic matrix is insufficient, and the modified straw powder cannot be well wrapped, so that the internal combination of the composite material is loose, the mechanical property is reduced, and therefore, the addition amount of the modified straw powder is selected to be 30%.
Test example 3
Testing of flame retardant Properties, degradability, tensile Strength
The flame retardant performance test method comprises the following steps: and testing limiting oxygen index of the starch-based degradable polypropylene composite material obtained in each example and the materials of comparative examples 24-27 according to ISO4589-2 standard.
The degradation performance testing method comprises the following steps: the starch-based degradable polypropylene composite material obtained in each example and the material of comparative examples 24-27 are subjected to die pressing and cutting into sheets of 20mm by 20mm to serve as samples, the samples are placed in beakers filled with the same soil, the same depth is kept, the temperature is kept at 30 ℃, the water content of the soil is kept at 20%, the samples are taken out after 30 days, washed and dried, and then weighed, and the degradation rate=1- (after 30 days, mass/initial mass) is calculated.
Tensile strength test method: the starch-based degradable polypropylene composite material obtained in each example and the materials of comparative examples 24-27 were tested for tensile strength according to GB/T1040.1-2006, the tensile speed was 2mm/min, and the results are shown in Table 3.
As can be seen from the comparison of the experimental data of examples 1-3 and comparative examples 24-27 in Table 3, the starch-based degradable polypropylene composite material prepared by the invention has good flame retardant property, degradability and tensile strength.
As can be found by comparing examples 1-3 with comparative example 24, the degradation rate can be effectively improved by adding soluble starch in the preparation process of starch-based polypropylene.
By comparing examples 1-3 with comparative example 25, it can be found that the addition of the organosilicon monomer during the preparation of starch-based polypropylene can generate silicon dioxide flame retardance at high temperature, thereby improving flame retardance, and the organosilicon monomer introduces a large number of silicon-hydrogen bond branched chains on the starch-based polypropylene, and can react with carbon-carbon double bonds on the modified straw powder through hydrosilylation reaction to form a crosslinked network structure, thereby improving tensile strength.
By comparing the examples 1-3 with the comparative example 26, it can be found that the wheat straw powder is pretreated to dissolve substances such as monosaccharides and polysaccharides in the fibers, so that the structure of the crop straw powder is destroyed, the fiber bundles are separated, starch-based polypropylene enters between the fiber bundles, the starch-based polypropylene wraps the crop straw powder better, and meanwhile, more active sites are exposed to facilitate subsequent modification, more polyphosphate branched chains are generated, and the flame retardant property and the tensile strength are improved.
As can be found by comparing examples 1-3 with comparative example 27, the pretreatment straw powder is modified, 4-dihydroxybiphenyl and allylphosphine dichloride are dehydrochlorinated and polycondensed on the surface of the pretreatment straw powder to generate a polyphosphate branched chain, and when the pretreatment straw powder is combusted, the polyphosphate branched chain is thermally decomposed to generate phosphoric acid, polyphosphoric acid and the like to promote the crosslinking of the starch-based degradable polypropylene composite material to generate a compact carbon layer to cover the surface, so that the volatile combustible gas and air are blocked to exchange gas, the heat transfer is inhibited, the further thermal decomposition of the starch-based degradable polypropylene composite material is prevented, and the flame retardant property is improved; and the polyphosphate branched chain contains a large number of carbon-carbon double bonds, and can be subjected to silicon-hydrogen reaction crosslinking with silicon-hydrogen bonds on starch-based polypropylene, so that the tensile strength is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (5)
1. The preparation method of the starch-based degradable polypropylene composite material is characterized in that the starch-based degradable polypropylene composite material is prepared by mixing and hot pressing starch-based polypropylene and modified straw powder;
the starch-based polypropylene is formed by polymerizing soluble starch, an organosilicon monomer and propylene;
the organic silicon monomer is prepared by reacting D4H cyclotetrasiloxane and vinyl pentamethyl disiloxane;
the modified straw powder is prepared by the steps of preparing pretreated straw powder from crop straw powder through sodium hydroxide solution digestion, preparing the pretreated straw powder by reacting the pretreated straw powder with allyl phosphine dichloride, and carrying out dehydrochlorination polycondensation reaction on the surface of the pretreated straw powder by 4, 4-dihydroxybiphenyl and allyl phosphine dichloride;
The preparation method comprises the following preparation steps:
(1) Uniformly mixing D4H cyclotetrasiloxane and vinyl pentamethyldisiloxane according to a molar ratio of 1:1, adding sulfuric acid with a mass fraction of 98% which is 0.06-0.08 times that of the D4H cyclotetrasiloxane, stirring and reacting for 8-10 hours at 40-50 ℃ and 200-300 r/min, adding sodium bicarbonate to adjust the pH value to 6.8-7.2, filtering to remove solids, and drying for 10-12 hours at 110-120 ℃ and 50-100 Pa to obtain an organosilicon monomer; uniformly mixing soluble starch, an organosilicon monomer, pure water, ethanol and tetrahydrofuran according to the mass ratio of (0.3-0.5) (40-50) in a nitrogen atmosphere, adding the mixture into a high-pressure reaction kettle, enabling the addition to reach 60-70% of the capacity of the reaction kettle, stirring for 10-15 min at the temperature of 10-20 ℃ at 200-300 r/min, adjusting the pH value to 5 by using a hydrochloric acid solution with the mass fraction of 10%, heating to 40 ℃, introducing propylene to enable the pressure to reach 0.5-0.7 MPa, continuously introducing the mixture until the mass of the introduced propylene is 3 times that of the soluble starch, stopping introducing the mixture until the mass of the introduced propylene is 1:40-60, uniformly mixing cerium ammonium nitrate and pure water which are 0.03 times that of the soluble starch into a cerium ammonium nitrate solution according to the mass ratio of 1:40-60, reacting for 1.5h, opening the reaction kettle, placing the reaction kettle at the temperature of 40-50 ℃ at the constant speed, drying under the pressure of 100-500 Pa until no liquid is present, and washing the polypropylene with ethanol for 3 times to obtain acetone-based starch;
(2) Soaking crop straw powder in pure water, standing for 10-12 hours at 20-30 ℃, then placing in a sodium hydroxide solution with mass fraction of 5%, steaming for 2-3 hours at 90-100 ℃, filtering, washing to be neutral by using the pure water, and drying for 8-10 hours at 60-70 ℃ to obtain pretreated straw powder; uniformly mixing the pretreated straw powder and allylphosphine dichloride according to the mass ratio of 1:2-3, adding anhydrous aluminum chloride with the mass of 0.003-0.004 times of that of the pretreated straw powder, stirring and reacting for 50-60 min at 60-70 ℃ and 200-300 r/min in a nitrogen atmosphere, filtering, washing for 3-5 times with pure water, and drying for 8-10 h at 60-70 ℃ to obtain the pre-modified straw powder; uniformly mixing pre-modified straw powder, 4-dihydroxybiphenyl and anhydrous aluminum chloride according to the mass ratio of 1 (3-4) (0.03-0.04), heating to 60-70 ℃ under stirring at 200-300 r/min in a nitrogen atmosphere, dropwise adding allyl phosphine dichloride at a constant speed within 25-30 min, continuing to react for 30-40 min after the dropwise adding is finished, heating to 90-100 ℃ and continuing to stir for 50-60 min, heating to 150-160 ℃ and continuing to stir for 20-30 min, filtering while the mixture is hot, cooling to room temperature, washing with anhydrous ethanol and toluene for 3-5 times, and drying at 60-70 ℃ for 8-10 h to obtain modified straw powder;
(3) And (3) weighing starch-based polypropylene and modified straw powder, wherein the addition amount of the modified straw powder is 30% of the total mass, the balance is starch-based polypropylene, and chloroplatinic acid with the mass of 0.003-0.004 times of that of the starch-based polypropylene is added, and the starch-based polypropylene and the modified straw powder are placed in a three-dimensional linkage mixer to be uniformly mixed, and then poured into a mould for moulding, so that the starch-based degradable polypropylene composite material is prepared.
2. The method of claim 1, wherein the soluble starch in step (1) is analytically pure.
3. The method for preparing the starch-based degradable polypropylene composite material according to claim 1, wherein the crop straw powder in the step (2) is wheat straw powder with a mesh size of 80.
4. The method for preparing a starch-based degradable polypropylene composite material according to claim 1, wherein the compression molding method in the step (3) is as follows: pouring the mixture into a die for die pressing, wherein the die pressing temperature is 180 ℃, the die pressing pressure is 8MPa, the die pressing time is 30-40 min, and the die is opened and taken out after the pressure is kept unchanged and naturally cooled to room temperature.
5. Use of the starch-based degradable polypropylene composite material prepared by the preparation method of the starch-based degradable polypropylene composite material according to claim 1 in plastic products.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1568688A (en) * | 1977-03-10 | 1980-06-04 | Stadex Ab | Preparation of graft copolymers of starch |
| WO2003093395A1 (en) * | 2002-04-30 | 2003-11-13 | Niponi, Llc | Novel fire retardant materials and method for producing same |
| JP2007246602A (en) * | 2006-03-14 | 2007-09-27 | Asahi Kasei Corp | Method for producing modified silicone |
| CN114685796A (en) * | 2020-12-30 | 2022-07-01 | 四川苏博特新材料有限公司 | Modified silane, preparation method thereof and application thereof in early-strength alkali-free liquid accelerator |
| WO2023103114A1 (en) * | 2021-12-10 | 2023-06-15 | 王素贞 | Environmentally-friendly fully-biodegradable plastic and sheet product |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1568688A (en) * | 1977-03-10 | 1980-06-04 | Stadex Ab | Preparation of graft copolymers of starch |
| WO2003093395A1 (en) * | 2002-04-30 | 2003-11-13 | Niponi, Llc | Novel fire retardant materials and method for producing same |
| JP2007246602A (en) * | 2006-03-14 | 2007-09-27 | Asahi Kasei Corp | Method for producing modified silicone |
| CN114685796A (en) * | 2020-12-30 | 2022-07-01 | 四川苏博特新材料有限公司 | Modified silane, preparation method thereof and application thereof in early-strength alkali-free liquid accelerator |
| WO2023103114A1 (en) * | 2021-12-10 | 2023-06-15 | 王素贞 | Environmentally-friendly fully-biodegradable plastic and sheet product |
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