CN113563640A - Elastic filling particles for biomass artificial turf - Google Patents
Elastic filling particles for biomass artificial turf Download PDFInfo
- Publication number
- CN113563640A CN113563640A CN202110957781.3A CN202110957781A CN113563640A CN 113563640 A CN113563640 A CN 113563640A CN 202110957781 A CN202110957781 A CN 202110957781A CN 113563640 A CN113563640 A CN 113563640A
- Authority
- CN
- China
- Prior art keywords
- biomass
- parts
- styrene
- mass
- artificial turf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- 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
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C13/00—Pavings or foundations specially adapted for playgrounds or sports grounds; Drainage, irrigation or heating of sports grounds
- E01C13/08—Surfaces simulating grass ; Grass-grown sports grounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention discloses biomass artificial turf elastic filling particles, and relates to the field of filling particles for artificial turf. When the biomass artificial turf elastic filling particles are prepared, modified biomass, modified styrene, a polyethylene octene co-elastomer and thermoplastic polyurethane rubber are mixed and extruded by an extruder to prepare the biomass artificial turf elastic filling particles; the modified biomass is prepared by grafting hexamethylene diisocyanate on biomass and then coating the biomass with dopamine; the modified styrene is prepared by copolymerizing maleic anhydride and styrene to prepare a hyperbranched styrene maleic anhydride copolymer and then esterifying the hyperbranched styrene maleic anhydride copolymer. The biomass artificial turf elastic filling particles prepared by the invention not only have good binding property of the biomass component and the polymer component, but also have high elasticity.
Description
Technical Field
The invention relates to the field of filling particles for artificial lawns, in particular to an elastic filling particle for biomass artificial lawns.
Background
The court and the leisure lawn at home and abroad are two types of natural lawn and artificial lawn, and although the artificial lawn has higher one-time investment cost, the artificial lawn has been developed rapidly in the last ten years due to the characteristics of low later maintenance cost, high use frequency and the like. The rise of artificial turf has driven the development of "filler particles for artificial turf".
In response to carbon neutralization policy and carbon emission reduction policy, researches are being conducted to replace part of petroleum products with renewable resources, and the conventional filling particles in the past include crushed waste tires, EPDM elastic particles, TPE elastic particles and the like. The present application studies the preparation of filling particles for artificial turf with renewable biomass.
Disclosure of Invention
The invention aims to provide biomass artificial turf elastic filling particles to solve the problems in the background technology.
The biomass artificial turf elastic filling particle mainly comprises the following raw material components in parts by weight: 5-10 parts of modified styrene, 5-10 parts of polyethylene octene co-elastomer, 5-10 parts of thermoplastic polyurethane rubber, 20-50 parts of modified biomass, 20-40 parts of stone powder, 0-30 parts of white oil, 1-10 parts of compatilizer, 1-5 parts of pigment and 1-5 parts of anti-aging agent. .
Preferably, the modified biomass is prepared by grafting hexamethylene diisocyanate on biomass and then coating the biomass with dopamine; the modified styrene is prepared by copolymerizing maleic anhydride and styrene to prepare a hyperbranched styrene-maleic anhydride copolymer and then esterifying the hyperbranched styrene-maleic anhydride copolymer.
Preferably, the biomass is one or a mixture of wood powder, biomass, coffee grounds, cellulose and starch, and the particle size is 200-3000 meshes.
Preferably, the compatilizer is one or a mixture of ethylene-vinyl acetate copolymer, ethylene acrylic acid copolymer, grafted polypropylene and grafted elastomer.
Preferably, the anti-aging agent is one or a mixture of anti-aging agents UV-531 and UV-327.
Preferably, the biomass artificial turf elastic filling particles comprise the following raw material components in parts by weight: 5 parts of modified styrene, 5 parts of polyethylene octene co-elastomer, 5 parts of thermoplastic polyurethane rubber, 35 parts of modified biomass, 30 parts of stone powder, 15 parts of white oil, 5 parts of compatilizer, 5 parts of pigment and 5 parts of anti-aging agent.
Preferably, the preparation method of the biomass artificial turf elastic filling particles comprises the following specific steps:
(1) dispersing biomass in chlorobenzene with the mass 4 times that of the biomass, adding hexamethylene diisocyanate with the mass 0.3-0.5 time that of the biomass after uniformly stirring, heating to 110-125 ℃, adding dimethyltin with the mass 0.012-0.015 time that of the biomass, keeping the temperature, stirring and reacting for 3 hours at 800rpm, performing suction filtration, and washing for 3-5 times by using absolute ethyl alcohol to prepare pre-modified biomass;
(2) dispersing the pre-modified biomass in a dopamine solution 50 times of the mass of the pre-modified biomass, stirring at room temperature and 1200rpm for 20min, centrifuging to obtain a liquid containing the pre-modified biomass at the upper layer, filtering, washing with deionized water for 3-5 times, transferring to a vacuum oven, and drying at 80 ℃ for 8-10 h to obtain the modified biomass;
(3) styrene, azobisisobutyronitrile and vinyl benzyl mercaptan are mixed according to a mass ratio of 4: 1.2: 3.1, mixing and dispersing in toluene with the mass of 5.8 times of that of the styrene, and uniformly mixing to obtain a styrene toluene solution; mixing maleic anhydride and toluene with the mass of 8.5 times of that of the maleic anhydride, placing the mixture in a four-neck flask, heating to 70 ℃, stirring at 800rpm for 30min, dropwise adding a styrene toluene solution with the mass of 7.5 times of that of the maleic anhydride into the four-neck flask at the speed of 2L/min, carrying out heat preservation reaction for 6h, carrying out suction filtration, rinsing for 3min by using toluene with the temperature of 60-80 ℃, carrying out precipitation in ethanol with the mass of 30 times of that of the maleic anhydride, filtering the precipitate, and drying in a vacuum drying oven with the temperature of 30 ℃ to obtain a hyperbranched styrene-maleic anhydride copolymer;
(4) mixing hyperbranched styrene maleic anhydride copolymer, toluenesulfonic acid and butanone according to a mass ratio of 1: 0.1: 40, adding dodecanol with the mass of 3 times that of the toluenesulfonic acid, sequentially dripping methanol with the mass of 5 times that of the toluenesulfonic acid and n-butanol with the mass of 5 times that of the toluenesulfonic acid at 0.5L/min, stirring at 800rpm for 30min at room temperature, then carrying out evaporation concentration until the volume is reduced by 60%, carrying out precipitation separation by using petroleum ether, and drying in a vacuum drying oven at 30 ℃ to constant weight to prepare modified styrene;
(5) mixing modified styrene, polyethylene octene co-elastomer, thermoplastic polyurethane rubber, modified biomass, stone powder, white oil, compatilizer, pigment and anti-aging agent according to a formula ratio, placing the mixture into a mixing roll, and mixing for 2-8 min at 120-140 ℃; and (3) mixing, placing in a double-screw extruder, and extruding and granulating to obtain the biomass artificial turf elastic filling particles.
Preferably, in the step (1): the preparation method of the hexamethylene diisocyanate comprises the following steps: chlorobenzene, phosgene and phenyl isocyanate in a mass ratio of 9: 4.8: 1-9: 5: 1, placing the mixture into a four-neck flask, and dropwise adding a mixture of hexamethylene diamine and chlorobenzene, the mass of which is 11.5 times that of phenyl isocyanate, into the mixture of hexamethylene diamine and chlorobenzene at the temperature of 0 ℃ in an ice bath, wherein the mass ratio of the hexamethylene diamine to the chlorobenzene in the mixture of the hexamethylene diamine and the chlorobenzene is 1.15: and 5, dropwise adding for 2 hours, keeping the temperature for 2 hours, heating to 70-80 ℃, reacting for 2 hours, heating to 130 ℃ again, reacting for 6 hours, cooling to 90 ℃, introducing 1 hour of nitrogen at the speed of 1L/min, controlling the temperature to be 60-80 ℃, distilling under reduced pressure at 1.5-2 kPa, and collecting the fraction at 97-100 ℃ to prepare the hexamethylene diisocyanate.
Preferably, in the step (2): the preparation method of the dopamine solution comprises the following steps: dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH value of the dopamine-hydrochloric acid solution to 8.5 by using a buffer reagent to prepare a dopamine solution; the buffer solution is composed of hydrochloric acid with the mass fraction of 10% and tris (hydroxymethyl) aminomethane according to the mass ratio of 3: 1, and uniformly mixing.
Preferably, in the step (5): the temperature of the double-screw extruder is 120-180 ℃, and the temperature of extrusion molding is 160-230 ℃.
Compared with the prior art, the invention has the following beneficial effects:
when the biomass artificial turf elastic filling particles are prepared, modified biomass and modified styrene are mixed and extruded by an extruder; the modified biomass is prepared by grafting hexamethylene diisocyanate on biomass and then coating the biomass with dopamine; the modified styrene is prepared by copolymerizing maleic anhydride and styrene to prepare a hyperbranched styrene maleic anhydride copolymer and then esterifying the hyperbranched styrene maleic anhydride copolymer;
hydroxyl groups obtained by dissociating the surface of the biomass can react with isocyanate groups obtained on hexamethylene diisocyanate, the hexamethylene diisocyanate is grafted on the biomass, hydrophilic groups on the surface of the biomass are reduced, the polarity of the surface of the biomass is reduced, dopamine is polymerized into polydopamine on the surface after being coated by the dopamine, and the binding capacity of the biomass and modified styrene is enhanced; benzene ring and carbon hydrogen on the polydopamine produce the physics winding based on the methylene on the hexamethylene diisocyanate, make the connection firmly on the polydopamine layer on the living beings surface, wrap up long-chain hexamethylene diisocyanate on the living beings surface, become unevenness's nanostructure with the living beings surface, make between the modified biomass, not only rely on the cohesiveness to connect between modified biomass and the modified styrene, still possess nanometer adsorptivity, make between the modified biomass, be connected more closely between modified biomass and the modified styrene, strengthen the mechanical properties of packing the granule.
The hyperbranched styrene-maleic anhydride copolymer has a three-dimensional spherical stereo structure and multiple terminal groups, and can be used for prolonging the length of a carbon chain after esterification, winding the carbon chain on the uneven surface of the modified biomass, and carrying out physical winding while nano adsorption, so that pores between the modified biomass and the modified styrene have stronger hydrophobicity due to the extension of the carbon chain and the reduction of the pores, and the service life is prolonged; meanwhile, a fatty carbon chain is introduced into the molecular chain, so that the flexibility of the modified styrene is increased, the rigidity is weakened, and the elasticity of the filling particles is enhanced.
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.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method for testing the indexes of the biomass artificial turf elastic filler particles prepared in the examples and the comparative examples as follows:
the biomass artificial turf elastic filling particles prepared in the examples and the comparative examples are injected into a double-screw extruder again and extruded into block-shaped objects with the same size at 160 ℃ for testing;
rebound resilience: the block was tested for resilience according to GB/T2941.
Breaking strength: the blocks were tested for breaking strength according to GB/T3923.1 for the examples and comparative examples.
Hydrophobicity: the block was subjected to a water contact angle test.
Example 1
The biomass artificial turf elastic filling particle mainly comprises the following components in parts by weight:
5 parts of modified styrene, 5 parts of polyethylene octene co-elastomer, 5 parts of thermoplastic polyurethane rubber, 35 parts of modified biomass, 30 parts of stone powder, 15 parts of white oil, 5 parts of compatilizer, 5 parts of pigment and 5 parts of anti-aging agent.
The preparation method of the biomass artificial turf elastic filling particles comprises the following steps:
(1) dispersing bamboo powder in chlorobenzene with the mass 4 times that of the bamboo powder, adding hexamethylene diisocyanate with the mass 0.3 time that of the biomass after uniformly stirring, heating to 110 ℃, adding dimethyltin with the mass 0.012 time that of the bamboo powder, keeping the temperature, stirring and reacting for 3 hours at 800rpm, performing suction filtration, and washing for 3 times by using absolute ethyl alcohol to prepare pre-modified biomass;
(2) dispersing the pre-modified biomass in a dopamine solution 50 times of the mass of the pre-modified biomass, stirring at room temperature and 1200rpm for 20min, centrifuging to obtain a liquid containing the pre-modified biomass at the upper layer, filtering, washing with deionized water for 3 times, transferring to a vacuum oven, and drying at 80 ℃ for 8h to obtain the modified biomass;
(3) styrene, azobisisobutyronitrile and vinyl benzyl mercaptan are mixed according to a mass ratio of 4: 1.2: 3.1, mixing and dispersing in toluene with the mass of 5.8 times of that of the styrene, and uniformly mixing to obtain a styrene toluene solution; mixing maleic anhydride and toluene with the mass of 8.5 times of that of the maleic anhydride, placing the mixture in a four-neck flask, heating to 70 ℃, stirring at 800rpm for 30min, dropwise adding a styrene toluene solution with the mass of 7.5 times of that of the maleic anhydride into the four-neck flask at the speed of 2L/min, carrying out heat preservation reaction for 6h, carrying out suction filtration, leaching for 3min by using toluene with the temperature of 60 ℃, carrying out precipitation in ethanol with the mass of 30 times of that of the maleic anhydride, filtering the precipitate, and drying in a vacuum drying oven with the temperature of 30 ℃ to obtain a hyperbranched styrene-maleic anhydride copolymer;
(4) mixing hyperbranched styrene maleic anhydride copolymer, toluenesulfonic acid and butanone according to a mass ratio of 1: 0.1: 40, adding dodecanol with the mass of 3 times that of the toluenesulfonic acid, sequentially dripping methanol with the mass of 5 times that of the toluenesulfonic acid and n-butanol with the mass of 5 times that of the toluenesulfonic acid at 0.5L/min, stirring at 800rpm for 30min at room temperature, then carrying out evaporation concentration until the volume is reduced by 60%, carrying out precipitation separation by using petroleum ether, and drying in a vacuum drying oven at 30 ℃ to constant weight to prepare modified styrene;
(5) mixing modified styrene, polyethylene octene co-elastomer, thermoplastic polyurethane rubber, modified biomass, stone powder, white oil, compatilizer ethylene-vinyl acetate copolymer, pigment and anti-aging agent UV-531 according to a formula ratio, placing the mixture into a mixing roll, and mixing for 2-8 min at 120 ℃; and (3) mixing, placing in a double-screw extruder, and extruding and granulating to obtain the biomass artificial turf elastic filling particles.
Preferably, in the step (1): the preparation method of the hexamethylene diisocyanate comprises the following steps: chlorobenzene, phosgene and phenyl isocyanate in a mass ratio of 9: 4.8: 1, placing the mixture into a four-neck flask, and dropwise adding a mixture of hexamethylene diamine and chlorobenzene, the mass of which is 11.5 times that of phenyl isocyanate, into the mixture of hexamethylene diamine and chlorobenzene at the temperature of 0 ℃ in an ice bath, wherein the mass ratio of the hexamethylene diamine to the chlorobenzene in the mixture of the hexamethylene diamine and the chlorobenzene is 1.15: and 5, dropwise adding for 2 hours, keeping the temperature for 2 hours, heating to 70 ℃, reacting for 2 hours, heating to 130 ℃ again, reacting for 6 hours, cooling to 90 ℃, introducing 1 hour of nitrogen at the speed of 1L/min, controlling the temperature to be 60 ℃, distilling under reduced pressure of 1.5kPa, and collecting the fraction at 97-100 ℃ to obtain the hexamethylene diisocyanate.
Preferably, in the step (2): the preparation method of the dopamine solution comprises the following steps: dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH value of the dopamine-hydrochloric acid solution to 8.5 by using a buffer reagent to prepare a dopamine solution; the buffer solution is composed of hydrochloric acid with the mass fraction of 10% and tris (hydroxymethyl) aminomethane according to the mass ratio of 3: 1, and uniformly mixing.
Preferably, in the step (5): the temperature of the double-screw extruder is 160 ℃, and the temperature of extrusion molding is 190 ℃.
Example 2
The biomass artificial turf elastic filling particle mainly comprises the following components in parts by weight:
5 parts of modified styrene, 5 parts of polyethylene octene co-elastomer, 5 parts of thermoplastic polyurethane rubber, 35 parts of modified biomass, 30 parts of stone powder, 15 parts of white oil, 5 parts of compatilizer, 5 parts of pigment and 5 parts of anti-aging agent.
The preparation method of the biomass artificial turf elastic filling particles comprises the following steps:
(1) dispersing bamboo powder in chlorobenzene with the mass 4 times that of the bamboo powder, adding hexamethylene diisocyanate with the mass 0.3 time that of the biomass after uniformly stirring, heating to 110 ℃, adding dimethyltin with the mass 0.012 time that of the bamboo powder, keeping the temperature, stirring and reacting for 3 hours at 800rpm, performing suction filtration, and washing for 3 times by using absolute ethyl alcohol to prepare modified biomass;
(2) styrene, azobisisobutyronitrile and vinyl benzyl mercaptan are mixed according to a mass ratio of 4: 1.2: 3.1, mixing and dispersing in toluene with the mass of 5.8 times of that of the styrene, and uniformly mixing to obtain a styrene toluene solution; mixing maleic anhydride and toluene with the mass of 8.5 times of that of the maleic anhydride, placing the mixture in a four-neck flask, heating to 70 ℃, stirring at 800rpm for 30min, dropwise adding a styrene toluene solution with the mass of 7.5 times of that of the maleic anhydride into the four-neck flask at the speed of 2L/min, carrying out heat preservation reaction for 6h, carrying out suction filtration, leaching for 3min by using toluene with the temperature of 60 ℃, carrying out precipitation in ethanol with the mass of 30 times of that of the maleic anhydride, filtering the precipitate, and drying in a vacuum drying oven with the temperature of 30 ℃ to obtain a hyperbranched styrene-maleic anhydride copolymer;
(3) mixing hyperbranched styrene maleic anhydride copolymer, toluenesulfonic acid and butanone according to a mass ratio of 1: 0.1: 40, adding dodecanol with the mass of 3 times that of the toluenesulfonic acid, sequentially dripping methanol with the mass of 5 times that of the toluenesulfonic acid and n-butanol with the mass of 5 times that of the toluenesulfonic acid at 0.5L/min, stirring at 800rpm for 30min at room temperature, then carrying out evaporation concentration until the volume is reduced by 60%, carrying out precipitation separation by using petroleum ether, and drying in a vacuum drying oven at 30 ℃ to constant weight to prepare modified styrene;
(4) mixing modified styrene, polyethylene octene co-elastomer, thermoplastic polyurethane rubber, modified biomass, stone powder, white oil, compatilizer ethylene-vinyl acetate copolymer, pigment and anti-aging agent UV-531 according to a formula ratio, placing the mixture into a mixing roll, and mixing for 2-8 min at 120 ℃; and (3) mixing, placing in a double-screw extruder, and extruding and granulating to obtain the biomass artificial turf elastic filling particles.
Preferably, in the step (1): the preparation method of the hexamethylene diisocyanate comprises the following steps: chlorobenzene, phosgene and phenyl isocyanate in a mass ratio of 9: 4.8: 1, placing the mixture into a four-neck flask, and dropwise adding a mixture of hexamethylene diamine and chlorobenzene, the mass of which is 11.5 times that of phenyl isocyanate, into the mixture of hexamethylene diamine and chlorobenzene at the temperature of 0 ℃ in an ice bath, wherein the mass ratio of the hexamethylene diamine to the chlorobenzene in the mixture of the hexamethylene diamine and the chlorobenzene is 1.15: and 5, dropwise adding for 2 hours, keeping the temperature for 2 hours, heating to 70 ℃, reacting for 2 hours, heating to 130 ℃ again, reacting for 6 hours, cooling to 90 ℃, introducing 1 hour of nitrogen at the speed of 1L/min, controlling the temperature to be 60 ℃, distilling under reduced pressure of 1.5kPa, and collecting the fraction at 97-100 ℃ to obtain the hexamethylene diisocyanate.
Preferably, in the step (4): the temperature of the double-screw extruder is 160 ℃, and the temperature of extrusion molding is 190 ℃.
Example 3
The biomass artificial turf elastic filling particle mainly comprises the following components in parts by weight:
5 parts of modified styrene, 5 parts of polyethylene octene co-elastomer, 5 parts of thermoplastic polyurethane rubber, 35 parts of modified biomass, 30 parts of stone powder, 15 parts of white oil, 5 parts of compatilizer, 5 parts of pigment and 5 parts of anti-aging agent.
The preparation method of the biomass artificial turf elastic filling particles comprises the following steps:
(1) dispersing bamboo powder in chlorobenzene with the mass 4 times that of the bamboo powder, adding hexamethylene diisocyanate with the mass 0.3 time that of the biomass after uniformly stirring, heating to 110 ℃, adding dimethyltin with the mass 0.012 time that of the bamboo powder, keeping the temperature, stirring and reacting for 3 hours at 800rpm, performing suction filtration, and washing for 3 times by using absolute ethyl alcohol to prepare pre-modified biomass;
(2) dispersing the pre-modified biomass in a dopamine solution 50 times of the mass of the pre-modified biomass, stirring at room temperature and 1200rpm for 20min, centrifuging to obtain a liquid containing the pre-modified biomass at the upper layer, filtering, washing with deionized water for 3 times, transferring to a vacuum oven, and drying at 80 ℃ for 8h to obtain the modified biomass;
(3) styrene, azobisisobutyronitrile and vinyl benzyl mercaptan are mixed according to a mass ratio of 4: 1.2: 3.1, mixing and dispersing in toluene with the mass of 5.8 times of that of the styrene, and uniformly mixing to obtain a styrene toluene solution; mixing maleic anhydride and toluene with the mass of 8.5 times of that of the maleic anhydride, placing the mixture in a four-neck flask, heating to 70 ℃, stirring at 800rpm for 30min, dropwise adding a styrene toluene solution with the mass of 7.5 times of that of the maleic anhydride into the four-neck flask at the speed of 2L/min, carrying out heat preservation reaction for 6h, carrying out suction filtration, leaching for 3min by using toluene with the temperature of 60 ℃, carrying out precipitation in ethanol with the mass of 30 times of that of the maleic anhydride, filtering the precipitate, and drying in a vacuum drying oven with the temperature of 30 ℃ to obtain modified styrene;
(4) mixing modified styrene, polyethylene octene co-elastomer, thermoplastic polyurethane rubber, modified biomass, stone powder, white oil, compatilizer ethylene-vinyl acetate copolymer, pigment and anti-aging agent UV-531 according to a formula ratio, placing the mixture into a mixing roll, and mixing for 2-8 min at 120 ℃; and (3) mixing, placing in a double-screw extruder, and extruding and granulating to obtain the biomass artificial turf elastic filling particles.
Preferably, in the step (1): the preparation method of the hexamethylene diisocyanate comprises the following steps: chlorobenzene, phosgene and phenyl isocyanate in a mass ratio of 9: 4.8: 1, placing the mixture into a four-neck flask, and dropwise adding a mixture of hexamethylene diamine and chlorobenzene, the mass of which is 11.5 times that of phenyl isocyanate, into the mixture of hexamethylene diamine and chlorobenzene at the temperature of 0 ℃ in an ice bath, wherein the mass ratio of the hexamethylene diamine to the chlorobenzene in the mixture of the hexamethylene diamine and the chlorobenzene is 1.15: and 5, dropwise adding for 2 hours, keeping the temperature for 2 hours, heating to 70 ℃, reacting for 2 hours, heating to 130 ℃ again, reacting for 6 hours, cooling to 90 ℃, introducing 1 hour of nitrogen at the speed of 1L/min, controlling the temperature to be 60 ℃, distilling under reduced pressure of 1.5kPa, and collecting the fraction at 97-100 ℃ to obtain the hexamethylene diisocyanate.
Preferably, in the step (2): the preparation method of the dopamine solution comprises the following steps: dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH value of the dopamine-hydrochloric acid solution to 8.5 by using a buffer reagent to prepare a dopamine solution; the buffer solution is composed of hydrochloric acid with the mass fraction of 10% and tris (hydroxymethyl) aminomethane according to the mass ratio of 3: 1, and uniformly mixing.
Preferably, in the step (4): the temperature of the double-screw extruder is 160 ℃, and the temperature of extrusion molding is 190 ℃.
Comparative example
The biomass artificial turf elastic filling particle mainly comprises the following components in parts by weight:
5 parts of styrene, 5 parts of polyethylene octene co-elastomer, 5 parts of thermoplastic polyurethane rubber, 35 parts of biomass, 30 parts of stone powder, 15 parts of white oil, 5 parts of compatilizer, 5 parts of pigment and 5 parts of anti-aging agent.
The preparation method of the biomass artificial turf elastic filling particles comprises the following steps:
(1) mixing styrene, polyethylene octene co-elastomer, thermoplastic polyurethane rubber, biomass bamboo powder, stone powder, white oil, a compatilizer ethylene-vinyl acetate copolymer, pigment and an anti-aging agent UV-531 according to a formula ratio, placing the mixture into a mixing roll, and mixing for 2-8 min at 120 ℃; and (3) mixing, placing in a double-screw extruder, and extruding and granulating to obtain the biomass artificial turf elastic filling particles.
Preferably, in the step (1): the temperature of the double-screw extruder is 160 ℃, and the temperature of extrusion molding is 190 ℃.
Examples of effects
Table 1 below shows the results of performance analysis of the biomass artificial turf elastic infill particles using examples 1, 2, 3, 4 of the present invention and comparative example.
TABLE 1
| Rebound resilience (%) | Breaking Strength (g/tex) | Water contact Angle (°) | |
| Example 1 | 39 | 149.6 | 153 |
| Example 2 | 37 | 120.2 | 139 |
| Example 3 | 30 | 116.5 | 127 |
| Comparison ofExample (b) | 26 | 97.0 | 104 |
Compared with experimental data of comparative examples in table 1, experimental data of examples 1, 2 and 3 show that the biomass artificial turf elastic infill particle prepared in example 1 has good rebound resilience, breaking strength and hydrophobicity, which indicates that the modified biomass and styrene can enhance the rebound resilience and breaking strength of the biomass artificial turf elastic infill particle, and the biomass artificial turf elastic infill particle has strong binding force, small pores and good hydrophobicity; thus, a comparison of experimental data of example 1 and example 2 shows that the modified biomass coated with dopamine has a strong binding capacity with modified styrene and a high breaking strength, and the modified biomass not coated with dopamine has a weak binding capacity with modified styrene and pores, so that the breaking strength and the hydrophobicity are weak; from the comparison of the experimental data of the embodiment 1 and the embodiment 3, it can be found that after the hyperbranched styrene maleic anhydride copolymer is esterified, the hyperbranched styrene maleic anhydride copolymer has a plurality of terminal groups and a plurality of branched chains, the length of the carbon chain is prolonged after the esterification, the branched chain can be wound on the uneven surface of the modified biomass, and the modified biomass can be physically wound while nano-adsorbed, so that the pores between the modified biomass and the modified styrene are improved in breaking strength and hydrophobicity due to the prolongation of the carbon chain and the reduction of the pores.
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 attributes 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 (10)
1. The biomass artificial turf elastic filling particle is characterized by mainly comprising the following raw material components in parts by weight: 5-10 parts of modified styrene, 5-10 parts of polyethylene octene co-elastomer, 5-10 parts of thermoplastic polyurethane rubber, 20-50 parts of modified biomass, 20-40 parts of stone powder, 0-30 parts of white oil, 1-10 parts of compatilizer, 1-5 parts of pigment and 1-5 parts of anti-aging agent.
2. The biomass artificial turf elastic filling particle as claimed in claim 1, wherein the modified biomass is prepared by grafting hexamethylene diisocyanate on biomass and coating the biomass with dopamine; the modified styrene is prepared by copolymerizing maleic anhydride and styrene to prepare a hyperbranched styrene-maleic anhydride copolymer and then esterifying the hyperbranched styrene-maleic anhydride copolymer.
3. The biomass artificial turf elastic filling particle as claimed in claim 2, wherein the biomass is one or a mixture of wood powder, biomass, coffee grounds, cellulose and starch, and the particle size is 200-3000 meshes.
4. The biomass artificial turf elastic filling particle as claimed in claim 3, wherein the compatilizer is one or a mixture of ethylene-vinyl acetate copolymer, ethylene acrylic acid copolymer, grafted polypropylene and grafted elastomer.
5. The biomass artificial turf elastic filling particle as claimed in claim 4, wherein the anti-aging agent is one or a mixture of anti-aging agents UV-531 and UV-327.
6. The biomass artificial turf elastic filling particle as claimed in claim 5, wherein the biomass artificial turf elastic filling particle comprises the following raw material components in parts by weight: 5 parts of modified styrene, 5 parts of polyethylene octene co-elastomer, 5 parts of thermoplastic polyurethane rubber, 35 parts of modified biomass, 30 parts of stone powder, 15 parts of white oil, 5 parts of compatilizer, 5 parts of pigment and 5 parts of anti-aging agent.
7. The biomass artificial turf elastic filling particle as claimed in claim 6, wherein the preparation method of the biomass artificial turf elastic filling particle comprises the following specific steps:
(1) dispersing biomass in chlorobenzene with the mass 4 times that of the biomass, adding hexamethylene diisocyanate with the mass 0.3-0.5 time that of the biomass after uniformly stirring, heating to 110-125 ℃, adding dimethyltin with the mass 0.012-0.015 time that of the biomass, keeping the temperature, stirring and reacting for 3 hours at 800rpm, performing suction filtration, and washing for 3-5 times by using absolute ethyl alcohol to prepare pre-modified biomass;
(2) dispersing the pre-modified biomass in a dopamine solution 50 times of the mass of the pre-modified biomass, stirring at room temperature and 1200rpm for 20min, centrifuging to obtain a liquid containing the pre-modified biomass at the upper layer, filtering, washing with deionized water for 3-5 times, transferring to a vacuum oven, and drying at 80 ℃ for 8-10 h to obtain the modified biomass;
(3) styrene, azobisisobutyronitrile and vinyl benzyl mercaptan are mixed according to a mass ratio of 4: 1.2: 3.1, mixing and dispersing in toluene with the mass of 5.8 times of that of the styrene, and uniformly mixing to obtain a styrene toluene solution; mixing maleic anhydride and toluene with the mass of 8.5 times of that of the maleic anhydride, placing the mixture in a four-neck flask, heating to 70 ℃, stirring at 800rpm for 30min, dropwise adding a styrene toluene solution with the mass of 7.5 times of that of the maleic anhydride into the four-neck flask at the speed of 2L/min, carrying out heat preservation reaction for 6h, carrying out suction filtration, rinsing for 3min by using toluene with the temperature of 60-80 ℃, carrying out precipitation in ethanol with the mass of 30 times of that of the maleic anhydride, filtering the precipitate, and drying in a vacuum drying oven with the temperature of 30 ℃ to obtain a hyperbranched styrene-maleic anhydride copolymer;
(4) mixing hyperbranched styrene maleic anhydride copolymer, toluenesulfonic acid and butanone according to a mass ratio of 1: 0.1: 40, adding dodecanol with the mass of 3 times that of the toluenesulfonic acid, sequentially dripping methanol with the mass of 5 times that of the toluenesulfonic acid and n-butanol with the mass of 5 times that of the toluenesulfonic acid at 0.5L/min, stirring at 800rpm for 30min at room temperature, then carrying out evaporation concentration until the volume is reduced by 60%, carrying out precipitation separation by using petroleum ether, and drying in a vacuum drying oven at 30 ℃ to constant weight to prepare modified styrene;
(5) mixing modified styrene, polyethylene octene co-elastomer, thermoplastic polyurethane rubber, modified biomass, stone powder, white oil, compatilizer, pigment and anti-aging agent according to a formula ratio, placing the mixture into a mixing roll, and mixing for 2-8 min at 120-140 ℃; and (3) mixing, placing in a double-screw extruder, and extruding and granulating to obtain the biomass artificial turf elastic filling particles.
8. The biomass artificial turf elastic infill particle of claim 7, wherein in step (1): the preparation method of the hexamethylene diisocyanate comprises the following steps: chlorobenzene, phosgene and phenyl isocyanate in a mass ratio of 9: 4.8: 1-9: 5: 1, placing the mixture into a four-neck flask, and dropwise adding a mixture of hexamethylene diamine and chlorobenzene, the mass of which is 11.5 times that of phenyl isocyanate, into the mixture of hexamethylene diamine and chlorobenzene at the temperature of 0 ℃ in an ice bath, wherein the mass ratio of the hexamethylene diamine to the chlorobenzene in the mixture of the hexamethylene diamine and the chlorobenzene is 1.15: and 5, dropwise adding for 2 hours, keeping the temperature for 2 hours, heating to 70-80 ℃, reacting for 2 hours, heating to 130 ℃ again, reacting for 6 hours, cooling to 90 ℃, introducing 1 hour of nitrogen at the speed of 1L/min, controlling the temperature to be 60-80 ℃, distilling under reduced pressure at 1.5-2 kPa, and collecting the fraction at 97-100 ℃ to prepare the hexamethylene diisocyanate.
9. The biomass artificial turf elastic infill particle of claim 7, wherein in step (2): the preparation method of the dopamine solution comprises the following steps: dispersing dopamine hydrochloride in deionized water to prepare a dopamine-hydrochloric acid solution with the concentration of 2g/L, and adjusting the pH value of the dopamine-hydrochloric acid solution to 8.5 by using a buffer reagent to prepare a dopamine solution; the buffer solution is composed of hydrochloric acid with the mass fraction of 10% and tris (hydroxymethyl) aminomethane according to the mass ratio of 3: 1, and uniformly mixing.
10. The biomass artificial turf resilient infill particle of claim 7, wherein in step (5): the temperature of the double-screw extruder is 120-180 ℃, and the temperature of extrusion molding is 160-230 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110957781.3A CN113563640A (en) | 2021-08-20 | 2021-08-20 | Elastic filling particles for biomass artificial turf |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110957781.3A CN113563640A (en) | 2021-08-20 | 2021-08-20 | Elastic filling particles for biomass artificial turf |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113563640A true CN113563640A (en) | 2021-10-29 |
Family
ID=78172180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110957781.3A Pending CN113563640A (en) | 2021-08-20 | 2021-08-20 | Elastic filling particles for biomass artificial turf |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113563640A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114045042A (en) * | 2021-11-22 | 2022-02-15 | 益阳桃花江竹业发展有限公司 | Bamboo-plastic composite material for container bottom plate and preparation method thereof |
| CN116554398A (en) * | 2023-07-10 | 2023-08-08 | 山东万亿体育健康服务有限公司 | Artificial turf material with high buffering performance and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19837234A1 (en) * | 1998-08-17 | 2000-02-24 | Few Chemicals Gmbh Wolfen Chem | Polymer composition and process for its manufacture |
| CN102464850A (en) * | 2010-11-18 | 2012-05-23 | 上海锦湖日丽塑料有限公司 | Natural fiber-reinforced styrene maleic anhydride copolymer composition and preparation method thereof |
| US20130131221A1 (en) * | 2010-06-29 | 2013-05-23 | Eastman Chemical Company | Cellulose ester/elastomer compositions |
| CN104788597A (en) * | 2014-01-22 | 2015-07-22 | 上海飞凯光电材料股份有限公司 | Preparation method for styrene maleic anhydride ester |
| CN105111716A (en) * | 2015-08-26 | 2015-12-02 | 安徽电缆股份有限公司 | Warping-resistant anti-fatigue TPE elastic material for cable of nuclear power station and preparation method of warping-resistant anti-fatigue TPE elastic material |
| WO2016015508A1 (en) * | 2014-07-31 | 2016-02-04 | 南京工业大学 | Straw biomass modification and method of use |
| CN107082973A (en) * | 2017-04-21 | 2017-08-22 | 仇颖超 | A kind of preparation method of outdoor garden Wood plastic composite |
| CN107090186A (en) * | 2017-06-25 | 2017-08-25 | 北京林业大学 | A kind of preparation method based on the enhanced bamboo-plastic composite material of dopamine |
| CN107286629A (en) * | 2016-04-05 | 2017-10-24 | 万华化学集团股份有限公司 | A kind of environment-friendly type chinampa filling thermoplastic elastomer (TPE) particle and preparation method thereof |
| US20180346708A1 (en) * | 2015-11-23 | 2018-12-06 | Elix Polymers, S.L. | Thermoplastic abs composition reinforced with natural fibres |
| CN110105781A (en) * | 2019-04-26 | 2019-08-09 | 北京林业大学 | One kind enhancing bamboo powder/polyethylene interface compatibility technology based on the bionical interface modification of polyacrylamide base dopamine |
| CN112940467A (en) * | 2021-03-16 | 2021-06-11 | 晋江市新迪新材料科技有限公司 | Preparation method of bamboo-based fiber reinforced full-biodegradable composite material |
| CN112980158A (en) * | 2021-03-16 | 2021-06-18 | 晋江市新迪新材料科技有限公司 | Bamboo-based fiber reinforced full-biodegradable composite material |
-
2021
- 2021-08-20 CN CN202110957781.3A patent/CN113563640A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19837234A1 (en) * | 1998-08-17 | 2000-02-24 | Few Chemicals Gmbh Wolfen Chem | Polymer composition and process for its manufacture |
| US20130131221A1 (en) * | 2010-06-29 | 2013-05-23 | Eastman Chemical Company | Cellulose ester/elastomer compositions |
| CN102464850A (en) * | 2010-11-18 | 2012-05-23 | 上海锦湖日丽塑料有限公司 | Natural fiber-reinforced styrene maleic anhydride copolymer composition and preparation method thereof |
| CN104788597A (en) * | 2014-01-22 | 2015-07-22 | 上海飞凯光电材料股份有限公司 | Preparation method for styrene maleic anhydride ester |
| WO2016015508A1 (en) * | 2014-07-31 | 2016-02-04 | 南京工业大学 | Straw biomass modification and method of use |
| CN105111716A (en) * | 2015-08-26 | 2015-12-02 | 安徽电缆股份有限公司 | Warping-resistant anti-fatigue TPE elastic material for cable of nuclear power station and preparation method of warping-resistant anti-fatigue TPE elastic material |
| US20180346708A1 (en) * | 2015-11-23 | 2018-12-06 | Elix Polymers, S.L. | Thermoplastic abs composition reinforced with natural fibres |
| CN107286629A (en) * | 2016-04-05 | 2017-10-24 | 万华化学集团股份有限公司 | A kind of environment-friendly type chinampa filling thermoplastic elastomer (TPE) particle and preparation method thereof |
| CN107082973A (en) * | 2017-04-21 | 2017-08-22 | 仇颖超 | A kind of preparation method of outdoor garden Wood plastic composite |
| CN107090186A (en) * | 2017-06-25 | 2017-08-25 | 北京林业大学 | A kind of preparation method based on the enhanced bamboo-plastic composite material of dopamine |
| CN110105781A (en) * | 2019-04-26 | 2019-08-09 | 北京林业大学 | One kind enhancing bamboo powder/polyethylene interface compatibility technology based on the bionical interface modification of polyacrylamide base dopamine |
| CN112940467A (en) * | 2021-03-16 | 2021-06-11 | 晋江市新迪新材料科技有限公司 | Preparation method of bamboo-based fiber reinforced full-biodegradable composite material |
| CN112980158A (en) * | 2021-03-16 | 2021-06-18 | 晋江市新迪新材料科技有限公司 | Bamboo-based fiber reinforced full-biodegradable composite material |
Non-Patent Citations (2)
| Title |
|---|
| 周家达等: "苯乙烯马来酸酐共聚物的阳离子化改性及其对颜料的分散", 《化工新型材料》, no. 03, 25 March 2007 (2007-03-25), pages 72 - 74 * |
| 益小苏主编: "《生物质树脂、纤维及生物复合材料》", 31 August 2017, 中国建材工业出版社, pages: 15 - 16 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114045042A (en) * | 2021-11-22 | 2022-02-15 | 益阳桃花江竹业发展有限公司 | Bamboo-plastic composite material for container bottom plate and preparation method thereof |
| CN114045042B (en) * | 2021-11-22 | 2022-11-25 | 益阳桃花江竹业发展有限公司 | Bamboo-plastic composite material for container bottom plate and preparation method thereof |
| CN116554398A (en) * | 2023-07-10 | 2023-08-08 | 山东万亿体育健康服务有限公司 | Artificial turf material with high buffering performance and preparation method thereof |
| CN116554398B (en) * | 2023-07-10 | 2023-11-07 | 山东万亿体育健康服务有限公司 | Artificial turf material with high buffering performance and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113563640A (en) | Elastic filling particles for biomass artificial turf | |
| Ogino et al. | Synthesis of monodisperse macroreticular styrene-divinylbenzene gel particles by a single-step swelling and polymerization method | |
| CN102604368B (en) | NCO replaced crosslinking cured joint filling material for concrete pavement | |
| CN103214629A (en) | Antistatic agent for dacron textile and preparation method of antistatic agent | |
| CN114891183B (en) | Aqueous polyurethane modified starch dispersion liquid and preparation method thereof | |
| CN111040125B (en) | Composite fulvic acid antibacterial sponge matrix and preparation method and application thereof | |
| CN112250890B (en) | Method for preparing chitosan/aramid nanofiber composite hydrogel by standing method | |
| Cui et al. | Preparation of natural rubber based semi-IPNs superabsorbent and its adsorption behavior for ammonium | |
| CN110964150A (en) | Acrylamide-alginate sand-fixing water-retaining agent and preparation method thereof | |
| CN112300419A (en) | Preparation method of cellulose aerogel with environmental responsiveness | |
| CN105331030A (en) | High-elasticity weather-resistant TPE telescopic water pipe and preparation method thereof | |
| CN110273227B (en) | Preparation method of flexible Janus electrostatic spinning fiber membrane with automatic moisture-guiding function | |
| CN113853869B (en) | Spray seeding agent and application thereof | |
| CN109705398A (en) | A kind of polyolefin film non-migratory hydrophilic antifogging masterbatch and its preparation | |
| CN108753137A (en) | A kind of environmental protection equipment surface aging resistant coating | |
| CN109824820B (en) | Composite high-molecular water-absorbing resin containing nitrogen and potassium and preparation method thereof | |
| JP3347695B2 (en) | Microbial adsorbent carrier, method for producing the carrier, and method for forming film on carrier surface | |
| CN110358033B (en) | Monodisperse amphoteric ion exchange thermosetting resin microsphere and preparation method thereof | |
| CN108993440B (en) | Preparation method of oil-absorbing resin ball for adsorbing marine floating oil | |
| CN111171494B (en) | Impact-resistant shear-thickening polyurethane hydrogel and preparation method thereof | |
| CN114456349B (en) | Microporous polyurethane plastic particle material and preparation method and application thereof | |
| CN106566454A (en) | Antibacterial and conductive silane end-capping polyurethane sealing glue and preparation method thereof | |
| CN108774375B (en) | Preparation method of degradable high-water-retention liquid mulching film dry powder | |
| CN111019326A (en) | Wear-resistant easily-degradable E-TPU beads and preparation method thereof | |
| CN110054746A (en) | A kind of method that click chemistry quickly prepares micrometer level porous polymer microballoon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211029 |
|
| RJ01 | Rejection of invention patent application after publication |