CN106189301A - A kind of flame-retardant wood-plastic material - Google Patents
A kind of flame-retardant wood-plastic material Download PDFInfo
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- CN106189301A CN106189301A CN201610545112.4A CN201610545112A CN106189301A CN 106189301 A CN106189301 A CN 106189301A CN 201610545112 A CN201610545112 A CN 201610545112A CN 106189301 A CN106189301 A CN 106189301A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a kind of flame-retardant wood-plastic material, in units of weight portion, including following raw material: mulberry wood powder 30 60 parts, corn stalk powder 20 40 parts, 8 12 parts of old and useless newspaper powder, waste and old packaging bag plastic pellet 6 10 parts, filler 68 parts, synthetics 46 parts, lubricant 12 parts, antimildew and antibacterial agent 12 parts, hygroscopic agent 12 parts, fire retardant 24 parts, smoke suppressant 24 parts, binding agent 6 10 parts.The flame-retardant wood-plastic material of the present invention can be widely applied to hotel, restaurant, building decoration and fitment, good flame retardation effect, it is impossible to burns and forms flame, stable and reliable for performance.
Description
Technical field
The invention belongs to Wood-plastic material technology of preparing and field of Environment Protection, be specifically related to a kind of flame-retardant wood-plastic material.
Background technology
Wood plastic composite (WPC), is a kind of main by answering that material and plastics based on timber or cellulose are made
Condensation material, it is simply that by a certain proportion of wood fiber (such as wood powder, powder of straw, cotton stalk powder, bamboo powder, shell powder etc.) through pre-place
Reason is allowed to a kind of new material being combined into thermoplastic polymer resin or other materials;The both environmental protections of this new material
There is again good mechanical stability, but the two big raw material wood fiber of composition wood plastic composite and polyolefin are all inflammabilities
Material, is also combustible material for this this composite, and the fire resistance giving wood plastic composite good is that this materials application is sent out
The needs of exhibition;Individually the fire-retardant research to timber and the wood fiber has a lot, typically has phosphorus-nitrogenated flame retardant;Boron flame retardant;Contain
Halogen fire retardant;Other inorganic salts etc.;But main based on phosphorus-nitrogenated flame retardant it is considered to be optimum wood fire retardant,
Phosphorus, two kinds of elements of nitrogen play synergism in wood fire retardant and improve flame retardant effect;But these fire retardants almost have one
Common feature, it is simply that reduce the thermal degradation temperature of the wood fiber significantly, this may result in and cannot be carried out adding of composite
Work;Research for polyolefin flame-retardant is also a lot, and its flame resistant method is frequently with halogen containing flame-retardant and antimony oxide (Sb2O3) join
Close and use;Metal hydroxides (Al (OH)3、Mg(OH)2) fire retardant;Expansibility flame-proof agent;Ammonium polyphosphate flame retardant etc.;Halogen
Fire-retardant is the focus of polyolefin flame-retardant research, expanding fire retardant polyolefin/Wood Fiber Composites is carried out dual fire-retardant be this
The focus of the fire-retardant research of composite;But the interpolation of fire retardant often deteriorates the mechanical property of composite, therefore to resistance
The research of the research flame-proof composite material of retardant composite material to study interface compatibility, heat stability and anti-flammability, to obtain simultaneously
Obtain preferable flame-proof composite material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of flame-retardant wood-plastic material, to solve fire retardant in prior art
Interpolation can deteriorate the problems such as the mechanical property of Wood-plastic material.The Wood-plastic material of the present invention can be widely applied to hotel, restaurant, building
Decorations, good flame retardation effect, it is impossible to burn and form flame, stable and reliable for performance.
In order to solve above technical problem, the present invention by the following technical solutions:
A kind of flame-retardant wood-plastic material, in units of weight portion, including following raw material: mulberry wood powder 30-60 part, corn stalk powder
20-40 part, old and useless newspaper powder 8-12 part, waste and old packaging bag plastic pellet 6-10 part, filler 6-8 part, synthetics 4-6 part, lubrication
Agent 1-2 part, antimildew and antibacterial agent 1-2 part, hygroscopic agent 1-2 part, fire retardant 2-4 part, smoke suppressant 2-4 part, binding agent 6-10 part;
Described filler is Kaolin;
Described synthetics is in units of weight portion, including following raw material: propellant 0.3-0.5 part, coupling agent 0.6-0.8 part, phase
Hold agent 0.4-0.6 part, antioxidant 0.3-0.5 part, regulator 0.3-0.6 part, hardening agent 0.3-0.5 part, flocculation agent 0.6-0.8
Part, plasticizer 0.6-0.9 part, stabilizer 0.3-0.4 part, terminator 0.3-0.4 part;
Described hardening agent is in units of weight portion, including following raw material: styrene 0.08-0.12 part, methylcrotonic acid methyl ester
0.08-0.12 part, vinylacetate 0.06-0.1 part, cobalt naphthenate 0.04-0.08 part, zinc chloride 0.04-0.08 part;
Described stabilizer is organic tin stabilizer;
Described lubricant is maleic anhydride grafted polyethylene wax;
Described antimildew and antibacterial agent is antimildew and antibacterial agent AEM5700-B;
Described hygroscopic agent is silica gel;
Described fire retardant is in units of weight portion, including following raw material: antimony oxide 0.4-0.8 part, chlordene cyclododecane
0.2-0.5 part, 2-chloroethyl-2-bromoethyl carboxylate 0.2-0.5 part, molybdenum oxide 0.4-0.7 part, Lauxite 0.2-0.5 part,
POLYPROPYLENE GLYCOL 0.2-0.4 part, bentonite 0.4-0.6 part;
Described smoke suppressant is in units of weight portion, including following raw material: dibutyl tin laurate 0.6-1.2 part, zirconium hydroxide
0.6-1.2 part, Pulvis Talci 0.4-0.8 part, ferrum oxide 0.4-0.8 part;
Described binding agent, with tapioca as raw material, carries out cross-linked graft reaction, then by elder generation with triglyceride, percarbamide
Carry out cross-linking reaction with potassium hydroxide and epoxychloropropane, then carry out pre-gelatinized reaction, be finally dried, pulverize, sieve and obtain;
The preparation method of described flame-retardant wood-plastic material, comprises the following steps:
S1: prepare synthetics, the preparation method of described synthetics, comprise the following steps:
S11: propellant, coupling agent, compatilizer, antioxidant mixing are warming up to 115-125 DEG C, are 100-300r/ at rotating speed
React 40-90 min under min, prepare material A;
S12: be warming up to 145-155 DEG C after adding regulator, hardening agent, flocculation agent mixing in the material A that step S11 prepares,
Under rotating speed is 300-400r/min, reacts 150-220 min, prepares material B;
S13: be cooled to 115-120 DEG C after adding plasticizer, stabilizer, terminator mixing in the material B that step S12 prepares,
Under rotating speed is 200-300r/min, reacts 60-100 min, prepares synthetics;
S2: prepare binding agent, the preparation method of described binding agent, comprise the following steps:
S21: compound concentration is para arrowroot slurry A of 20-23Be ';
S22: it is 1.5%-1.8% triglyceride, percarbamide that para arrowroot slurry A in step S21 adds concentration, then in temperature
Degree is for 26-34 DEG C, and speed of agitator is to carry out cross-linked graft reaction 0.6-1h under 50-80r/min, prepares slurry B;
S23: adding potassium hydroxide and epoxychloropropane in the slurry B of step S22, be then 32-36 DEG C in temperature, stirring turns
Speed, for carrying out cross-linking reaction 0.2-0.5h under 60-100r/min, prepares slurry C;
S24: be delivered to the slurry C of step S23 in cylindrical drier carry out pre-gelatinized and do at temperature is 140-145 DEG C
Dry, prepare the material D of water content≤6%;
S25: wind after the material D pulverizing of step S24, excessively 60-100 mesh sieve is delivered to whirlwind separator and is collected, prepare viscous
Mixture;
S3: by step S1 prepare synthetics, step S2 prepare binding agent, mulberry wood powder, corn stalk powder, old and useless newspaper
Powder, waste and old packaging bag plastic pellet, filler, lubricant, antimildew and antibacterial agent, hygroscopic agent, fire retardant, smoke suppressant put into pressure cooker
In, HIGH PRESSURE TREATMENT 0.5-0.8h under pressure is 12-15MPa, prepare raw material A;
S4: the raw material A that step S3 prepares is put into freezing 2-4h at temperature≤-30 DEG C, prepares raw material B;
S5: put in dehydrator by the raw material B that step S4 prepares, dries to water content≤5%, system at temperature is 78-80 DEG C
Obtain raw material C;
S6: raw material C step S5 prepared puts in blender, stirs 6-9min under rotating speed is 300-500r/min, prepares
Particle;
S7: put in extruder by the particle that step S6 prepares, extrudes at temperature is 185-190 DEG C, through cooling molding,
Prepare flame-retardant wood-plastic material.
Further, propellant described in step S11 is aerogel generating agent.
Further, coupling agent described in step S11 is furfural.
Further, compatilizer described in step S11 is acrylic type compatilizer.
Further, antioxidant described in step S11 is WINGSTAYL.
Further, regulator described in step S12 is JINHASS.
Further, flocculation agent described in step S12 is aluminium polychlorid.
Further, plasticizer described in step S13 is citrate.
Further, terminator described in step S13 is styrene.
Further, the mixed liquor cooling down employing described in step S7 is to be by water, ethanol, the mass ratio of ethyl salicylate
95-100:4-6:2-3 makes.
The method have the advantages that
(1) the flame-retardant wood-plastic material of the present invention has high flame resistance and smoke suppressing effect, at high temperature will not discharge poisonous and harmful
Material, it is to avoid the secondary injury to human body;
(2) heat-proof quality of the flame-retardant wood-plastic material of the present invention is the best, it is to avoid the scald to human body, and has well insulation
Property;
(3) the flame-retardant wood-plastic material of the present invention is fine and close, and mechanical property is good, extremely durable.
(4) the flame-retardant wood-plastic material of the present invention can be widely applied to hotel, restaurant, building decoration and fitment, good flame retardation effect,
Cannot burn and be formed flame, stable and reliable for performance.
Detailed description of the invention
For ease of being more fully understood that the present invention, being illustrated by following example, these embodiments belong to the present invention's
Protection domain, but it is not intended to protection scope of the present invention.
In an embodiment, described flame-retardant wood-plastic material, in units of weight portion, including following raw material: mulberry wood powder 30-60
Part, corn stalk powder 20-40 part, old and useless newspaper powder 8-12 part, waste and old packaging bag plastic pellet 6-10 part, filler 6-8 part, synthesis
Agent 4-6 part, lubricant 1-2 part, antimildew and antibacterial agent 1-2 part, hygroscopic agent 1-2 part, fire retardant 2-4 part, smoke suppressant 2-4 part, bonding
Agent 6-10 part;
Described filler is Kaolin;
Described synthetics is in units of weight portion, including following raw material: propellant 0.3-0.5 part, coupling agent 0.6-0.8 part, phase
Hold agent 0.4-0.6 part, antioxidant 0.3-0.5 part, regulator 0.3-0.6 part, hardening agent 0.3-0.5 part, flocculation agent 0.6-0.8
Part, plasticizer 0.6-0.9 part, stabilizer 0.3-0.4 part, terminator 0.3-0.4 part;
Described propellant is aerogel generating agent;
Described coupling agent is furfural;
Described compatilizer is acrylic type compatilizer;
Described antioxidant is WINGSTAYL;
Described regulator is JINHASS;
Described hardening agent is in units of weight portion, including following raw material: styrene 0.08-0.12 part, methylcrotonic acid methyl ester
0.08-0.12 part, vinylacetate 0.06-0.1 part, cobalt naphthenate 0.04-0.08 part, zinc chloride 0.04-0.08 part;
Described flocculation agent is aluminium polychlorid;
Described plasticizer is citrate;
Described stabilizer is organic tin stabilizer;
Described terminator is styrene;
Described lubricant is maleic anhydride grafted polyethylene wax;
Described antimildew and antibacterial agent is antimildew and antibacterial agent AEM5700-B;
Described hygroscopic agent is silica gel;
Described fire retardant is in units of weight portion, including following raw material: antimony oxide 0.4-0.8 part, chlordene cyclododecane
0.2-0.5 part, 2-chloroethyl-2-bromoethyl carboxylate 0.2-0.5 part, molybdenum oxide 0.4-0.7 part, Lauxite 0.2-0.5 part,
POLYPROPYLENE GLYCOL 0.2-0.4 part, bentonite 0.4-0.6 part;
Described smoke suppressant is in units of weight portion, including following raw material: dibutyl tin laurate 0.6-1.2 part, zirconium hydroxide
0.6-1.2 part, Pulvis Talci 0.4-0.8 part, ferrum oxide 0.4-0.8 part;
Described binding agent, with tapioca as raw material, carries out cross-linked graft reaction, then by elder generation with triglyceride, percarbamide
Carry out cross-linking reaction with potassium hydroxide and epoxychloropropane, then carry out pre-gelatinized reaction, be finally dried, pulverize, sieve and obtain;
The preparation method of described flame-retardant wood-plastic material, comprises the following steps:
S1: prepare synthetics, the preparation method of described synthetics, comprise the following steps:
S11: propellant, coupling agent, compatilizer, antioxidant mixing are warming up to 115-125 DEG C, are 100-300r/ at rotating speed
React 40-90 min under min, prepare material A;
S12: be warming up to 145-155 DEG C after adding regulator, hardening agent, flocculation agent mixing in the material A that step S11 prepares,
Under rotating speed is 300-400r/min, reacts 150-220 min, prepares material B;
S13: be cooled to 115-120 DEG C after adding plasticizer, stabilizer, terminator mixing in the material B that step S12 prepares,
Under rotating speed is 200-300r/min, reacts 60-100 min, prepares synthetics;
S2: prepare binding agent, the preparation method of described binding agent, comprise the following steps:
S21: compound concentration is para arrowroot slurry A of 20-23Be ';
S22: it is 1.5%-1.8% triglyceride, percarbamide that para arrowroot slurry A in step S21 adds concentration, then in temperature
Degree is for 26-34 DEG C, and speed of agitator is to carry out cross-linked graft reaction 0.6-1h under 50-80r/min, prepares slurry B;
S23: adding potassium hydroxide and epoxychloropropane in the slurry B of step S22, be then 32-36 DEG C in temperature, stirring turns
Speed, for carrying out cross-linking reaction 0.2-0.5h under 60-100r/min, prepares slurry C;
S24: be delivered to the slurry C of step S23 in cylindrical drier carry out pre-gelatinized and do at temperature is 140-145 DEG C
Dry, prepare the material D of water content≤6%;
S25: wind after the material D pulverizing of step S24, excessively 60-100 mesh sieve is delivered to whirlwind separator and is collected, prepare viscous
Mixture;
S3: by step S1 prepare synthetics, step S2 prepare binding agent, mulberry wood powder, corn stalk powder, old and useless newspaper
Powder, waste and old packaging bag plastic pellet, filler, lubricant, antimildew and antibacterial agent, hygroscopic agent, fire retardant, smoke suppressant put into pressure cooker
In, HIGH PRESSURE TREATMENT 0.5-0.8h under pressure is 12-15MPa, prepare raw material A;
S4: the raw material A that step S3 prepares is put into freezing 2-4h at temperature≤-30 DEG C, prepares raw material B;
S5: put in dehydrator by the raw material B that step S4 prepares, dries to water content≤5%, system at temperature is 78-80 DEG C
Obtain raw material C;
S6: raw material C step S5 prepared puts in blender, stirs 6-9min under rotating speed is 300-500r/min, prepares
Particle;
S7: put in extruder by the particle that step S6 prepares, extrudes at temperature is 185-190 DEG C, cold through mixed liquor
But molding, prepares flame-retardant wood-plastic material, and described mixed liquor is to be 95-100:4-6 by water, ethanol, the mass ratio of ethyl salicylate:
2-3 makes.
Below by more specifically embodiment, the present invention will be described.
Embodiment 1
A kind of flame-retardant wood-plastic material, in units of weight portion, including following raw material: mulberry wood powder 45 parts, corn stalk powder 30 parts,
10 parts of old and useless newspaper powder, waste and old packaging bag plastic pellet 8 parts, filler 7 parts, synthetics 5 parts, lubricant 1.5 parts, antimildew and antibacterial agent
1.5 parts, hygroscopic agent 1.5 parts, fire retardant 3 parts, smoke suppressant 3 parts, binding agent 8 parts;
Described filler is Kaolin;
Described synthetics is in units of weight portion, including following raw material: propellant 0.4 part, coupling agent 0.7 part, compatilizer 0.5
Part, antioxidant 0.4 part, regulator 0.5 part, hardening agent 0.4 part, flocculation agent 0.7 part, plasticizer 0.7 part, stabilizer 0.4 part,
Terminator 0.3 part;
Described propellant is aerogel generating agent;
Described coupling agent is furfural;
Described compatilizer is acrylic type compatilizer;
Described antioxidant is WINGSTAYL;
Described regulator is JINHASS;
Described hardening agent is in units of weight portion, including following raw material: styrene 0.1 part, methylcrotonic acid methyl ester 0.1 part, vinegar
Vinyl acetate 0.08 part, cobalt naphthenate 0.06 part, zinc chloride 0.06 part;
Described flocculation agent is aluminium polychlorid;
Described plasticizer is citrate;
Described stabilizer is organic tin stabilizer;
Described terminator is styrene;
Described lubricant is maleic anhydride grafted polyethylene wax;
Described antimildew and antibacterial agent is antimildew and antibacterial agent AEM5700-B;
Described hygroscopic agent is silica gel;
Described fire retardant is in units of weight portion, including following raw material: antimony oxide 0.6 part, chlordene cyclododecane 0.4 part,
2-chloroethyl-2-bromoethyl carboxylate 0.4 part, molybdenum oxide 0.5 part, Lauxite 0.3 part, POLYPROPYLENE GLYCOL 0.3 part, bentonite
0.5 part;
Described smoke suppressant is in units of weight portion, including following raw material: dibutyl tin laurate 0.9 part, zirconium hydroxide 0.9
Part, Pulvis Talci 0.6 part, ferrum oxide 0.6 part;
Described binding agent, with tapioca as raw material, carries out cross-linked graft reaction, then by elder generation with triglyceride, percarbamide
Carry out cross-linking reaction with potassium hydroxide and epoxychloropropane, then carry out pre-gelatinized reaction, be finally dried, pulverize, sieve and obtain;
The preparation method of described flame-retardant wood-plastic material, comprises the following steps:
S1: prepare synthetics, the preparation method of described synthetics, comprise the following steps:
S11: propellant, coupling agent, compatilizer, antioxidant mixing are warming up to 120 DEG C, react under rotating speed is 200r/min
65 min, prepare material A;
S12: be warming up to 150 DEG C after adding regulator, hardening agent, flocculation agent mixing in the material A that step S11 prepares, turning
Speed, for reacting 190 min under 400r/min, prepares material B;
S13: be cooled to 118 DEG C after adding plasticizer, stabilizer, terminator mixing in the material B that step S12 prepares, turning
Speed, for reacting 80 min under 300r/min, prepares synthetics;
S2: prepare binding agent, the preparation method of described binding agent, comprise the following steps:
S21: compound concentration is para arrowroot slurry A of 22Be ';
S22: it is 1.7% triglyceride, percarbamide that para arrowroot slurry A in step S21 adds concentration, then in temperature is
30 DEG C, speed of agitator is to carry out cross-linked graft reaction 0.8h under 70r/min, prepares slurry B;
S23: add potassium hydroxide and epoxychloropropane in the slurry B of step S22, is then 34 DEG C in temperature, speed of agitator
For carrying out cross-linking reaction 0.3h under 80r/min, prepare slurry C;
S24: be delivered to the slurry C of step S23 in cylindrical drier carry out pre-gelatinized and be dried at temperature is 143 DEG C,
Prepared water content is the material D of 6%;
S25: wind after the material D pulverizing of step S24, excessively 80 mesh sieves is delivered to whirlwind separator and is collected, prepare binding agent;
S3: by step S1 prepare synthetics, step S2 prepare binding agent, mulberry wood powder, corn stalk powder, old and useless newspaper
Powder, waste and old packaging bag plastic pellet, filler, lubricant, antimildew and antibacterial agent, hygroscopic agent, fire retardant, smoke suppressant put into pressure cooker
In, HIGH PRESSURE TREATMENT 0.6h under pressure is 14MPa, prepare raw material A;
S4: the raw material A that step S3 prepares is put into freezing 4h at temperature is-30 DEG C, prepares raw material B;
S5: put in dehydrator by the raw material B that step S4 prepares, drying at temperature is 80 DEG C to water content is 5%, prepares
Raw material C;
S6: raw material C step S5 prepared puts in blender, stirs 8min under rotating speed is 400r/min, prepares particle;
S7: put in extruder by the particle that step S6 prepares, extrudes at temperature is 188 DEG C, is cooled to through mixed liquor
Type, prepares flame-retardant wood-plastic material, and described mixed liquor is to be that 96:5:3 makes by water, ethanol, the mass ratio of ethyl salicylate.
Embodiment 2
A kind of flame-retardant wood-plastic material, in units of weight portion, including following raw material: mulberry wood powder 30 parts, corn stalk powder 20 parts,
8 parts of old and useless newspaper powder, waste and old packaging bag plastic pellet 6 parts, filler 6 parts, synthetics 4 parts, lubricant 1 part, antimildew and antibacterial agent 1
Part, hygroscopic agent 1 part, fire retardant 2 parts, smoke suppressant 2 parts, binding agent 6 parts;
Described filler is Kaolin;
Described synthetics is in units of weight portion, including following raw material: propellant 0.3 part, coupling agent 0.6 part, compatilizer 0.4
Part, antioxidant 0.3 part, regulator 0.3 part, hardening agent 0.3 part, flocculation agent 0.6 part, plasticizer 0.6 part, stabilizer 0.3 part,
Terminator 0.3 part;
Described propellant is aerogel generating agent;
Described coupling agent is furfural;
Described compatilizer is acrylic type compatilizer;
Described antioxidant is WINGSTAYL;
Described regulator is JINHASS;
Described hardening agent is in units of weight portion, including following raw material: styrene 0.08 part, methylcrotonic acid methyl ester 0.08 part,
Vinylacetate 0.06 part, cobalt naphthenate 0.04 part, zinc chloride 0.04 part;
Described flocculation agent is aluminium polychlorid;
Described plasticizer is citrate;
Described stabilizer is organic tin stabilizer;
Described terminator is styrene;
Described lubricant is maleic anhydride grafted polyethylene wax;
Described antimildew and antibacterial agent is antimildew and antibacterial agent AEM5700-B;
Described hygroscopic agent is silica gel;
Described fire retardant is in units of weight portion, including following raw material: antimony oxide 0.4 part, chlordene cyclododecane 0.2 part,
2-chloroethyl-2-bromoethyl carboxylate 0.2 part, molybdenum oxide 0.4 part, Lauxite 0.2 part, POLYPROPYLENE GLYCOL 0.2 part, bentonite
0.4 part;
Described smoke suppressant is in units of weight portion, including following raw material: dibutyl tin laurate 0.6 part, zirconium hydroxide 0.6
Part, Pulvis Talci 0.4 part, ferrum oxide 0.4 part;
Described binding agent, with tapioca as raw material, carries out cross-linked graft reaction, then by elder generation with triglyceride, percarbamide
Carry out cross-linking reaction with potassium hydroxide and epoxychloropropane, then carry out pre-gelatinized reaction, be finally dried, pulverize, sieve and obtain;
The preparation method of described flame-retardant wood-plastic material, comprises the following steps:
S1: prepare synthetics, the preparation method of described synthetics, comprise the following steps:
S11: propellant, coupling agent, compatilizer, antioxidant mixing are warming up to 115 DEG C, react under rotating speed is 100r/min
90 min, prepare material A;
S12: be warming up to 145 DEG C after adding regulator, hardening agent, flocculation agent mixing in the material A that step S11 prepares, turning
Speed, for reacting 220 min under 300r/min, prepares material B;
S13: be cooled to 115 DEG C after adding plasticizer, stabilizer, terminator mixing in the material B that step S12 prepares, turning
Speed, for reacting 100 min under 200r/min, prepares synthetics;
S2: prepare binding agent, the preparation method of described binding agent, comprise the following steps:
S21: compound concentration is para arrowroot slurry A of 20Be ';
S22: it is 1.5% triglyceride, percarbamide that para arrowroot slurry A in step S21 adds concentration, then in temperature is
26 DEG C, speed of agitator is to carry out cross-linked graft reaction 1h under 50r/min, prepares slurry B;
S23: add potassium hydroxide and epoxychloropropane in the slurry B of step S22, is then 32 DEG C in temperature, speed of agitator
For carrying out cross-linking reaction 0.5h under 60r/min, prepare slurry C;
S24: be delivered to the slurry C of step S23 in cylindrical drier carry out pre-gelatinized and be dried at temperature is 140 DEG C,
Prepared water content is the material D of 5%;
S25: wind after the material D pulverizing of step S24, excessively 60 mesh sieves is delivered to whirlwind separator and is collected, prepare binding agent;
S3: by step S1 prepare synthetics, step S2 prepare binding agent, mulberry wood powder, corn stalk powder, old and useless newspaper
Powder, waste and old packaging bag plastic pellet, filler, lubricant, antimildew and antibacterial agent, hygroscopic agent, fire retardant, smoke suppressant put into pressure cooker
In, HIGH PRESSURE TREATMENT 0.8h under pressure is 12MPa, prepare raw material A;
S4: the raw material A that step S3 prepares is put into freezing 3h at temperature is-40 DEG C, prepares raw material B;
S5: put in dehydrator by the raw material B that step S4 prepares, drying at temperature is 78 DEG C to water content is 4%, prepares
Raw material C;
S6: raw material C step S5 prepared puts in blender, stirs 9min under rotating speed is 300r/min, prepares particle;
S7: put in extruder by the particle that step S6 prepares, extrudes at temperature is 185 DEG C, is cooled to through mixed liquor
Type, prepares flame-retardant wood-plastic material, and described mixed liquor is to be that 95:4:2 makes by water, ethanol, the mass ratio of ethyl salicylate.
Embodiment 3
A kind of flame-retardant wood-plastic material, in units of weight portion, including following raw material: mulberry wood powder 60 parts, corn stalk powder 40 parts,
12 parts of old and useless newspaper powder, waste and old packaging bag plastic pellet 10 parts, filler 8 parts, synthetics 6 parts, lubricant 2 parts, antimildew and antibacterial agent 2
Part, hygroscopic agent 2 parts, fire retardant 4 parts, smoke suppressant 4 parts, binding agent 10 parts;
Described filler is Kaolin;
Described synthetics is in units of weight portion, including following raw material: propellant 0.5 part, coupling agent 0.8 part, compatilizer 0.6
Part, antioxidant 0.5 part, regulator 0.6 part, hardening agent 0.5 part, flocculation agent 0.8 part, plasticizer 0.9 part, stabilizer 0.4 part,
Terminator 0.4 part;
Described propellant is aerogel generating agent;
Described coupling agent is furfural;
Described compatilizer is acrylic type compatilizer;
Described antioxidant is WINGSTAYL;
Described regulator is JINHASS;
Described hardening agent is in units of weight portion, including following raw material: styrene 0.12 part, methylcrotonic acid methyl ester 0.12 part,
Vinylacetate 0.1 part, cobalt naphthenate 0.08 part, zinc chloride 0.08 part;
Described flocculation agent is aluminium polychlorid;
Described plasticizer is citrate;
Described stabilizer is organic tin stabilizer;
Described terminator is styrene;
Described lubricant is maleic anhydride grafted polyethylene wax;
Described antimildew and antibacterial agent is antimildew and antibacterial agent AEM5700-B;
Described hygroscopic agent is silica gel;
Described fire retardant is in units of weight portion, including following raw material: antimony oxide 0.8 part, chlordene cyclododecane 0.5 part,
2-chloroethyl-2-bromoethyl carboxylate 0.5 part, molybdenum oxide 0.7 part, Lauxite 0.5 part, POLYPROPYLENE GLYCOL 0.4 part, bentonite
0.6 part;
Described smoke suppressant is in units of weight portion, including following raw material: dibutyl tin laurate 1.2 parts, zirconium hydroxide 1.2
Part, Pulvis Talci 0.8 part, ferrum oxide 0.8 part;
Described binding agent, with tapioca as raw material, carries out cross-linked graft reaction, then by elder generation with triglyceride, percarbamide
Carry out cross-linking reaction with potassium hydroxide and epoxychloropropane, then carry out pre-gelatinized reaction, be finally dried, pulverize, sieve and obtain;
The preparation method of described flame-retardant wood-plastic material, comprises the following steps:
S1: prepare synthetics, the preparation method of described synthetics, comprise the following steps:
S11: propellant, coupling agent, compatilizer, antioxidant mixing are warming up to 125 DEG C, react under rotating speed is 300r/min
40 min, prepare material A;
S12: be warming up to 155 DEG C after adding regulator, hardening agent, flocculation agent mixing in the material A that step S11 prepares, turning
Speed, for reacting 150 min under 400r/min, prepares material B;
S13: be cooled to 120 DEG C after adding plasticizer, stabilizer, terminator mixing in the material B that step S12 prepares, turning
Speed, for reacting 60 min under 300r/min, prepares synthetics;
S2: prepare binding agent, the preparation method of described binding agent, comprise the following steps:
S21: compound concentration is para arrowroot slurry A of 23Be ';
S22: it is 1.8% triglyceride, percarbamide that para arrowroot slurry A in step S21 adds concentration, then in temperature is
34 DEG C, speed of agitator is to carry out cross-linked graft reaction 0.6h under 80r/min, prepares slurry B;
S23: add potassium hydroxide and epoxychloropropane in the slurry B of step S22, is then 36 DEG C in temperature, speed of agitator
For carrying out cross-linking reaction 0.2h under 100r/min, prepare slurry C;
S24: be delivered to the slurry C of step S23 in cylindrical drier carry out pre-gelatinized and be dried at temperature is 145 DEG C,
Prepared water content is the material D of 4%;
S25: wind after the material D pulverizing of step S24, excessively 100 mesh sieves is delivered to whirlwind separator and is collected, prepare bonding
Agent;
S3: by step S1 prepare synthetics, step S2 prepare binding agent, mulberry wood powder, corn stalk powder, old and useless newspaper
Powder, waste and old packaging bag plastic pellet, filler, lubricant, antimildew and antibacterial agent, hygroscopic agent, fire retardant, smoke suppressant put into pressure cooker
In, HIGH PRESSURE TREATMENT 0.5h under pressure is 15MPa, prepare raw material A;
S4: the raw material A that step S3 prepares is put into freezing 2h at temperature is-50 DEG C, prepares raw material B;
S5: put in dehydrator by the raw material B that step S4 prepares, drying at temperature is 80 DEG C to water content is 3%, prepares
Raw material C;
S6: raw material C step S5 prepared puts in blender, stirs 6min under rotating speed is 500r/min, prepares particle;
S7: put in extruder by the particle that step S6 prepares, extrudes at temperature is 190 DEG C, is cooled to through mixed liquor
Type, prepares flame-retardant wood-plastic material, and described mixed liquor is to be that 100:6:3 makes by water, ethanol, the mass ratio of ethyl salicylate
's.
The composite can be widely applied to hotel, restaurant, building decoration and fitment, good flame retardation effect, it is impossible to burn and form fire
Flame, stable and reliable for performance, its performance indications are tested by following fire resistance test experiments and Mechanics Performance Testing and are given:
(1) fire resistance test experiments
Sample prepared by above-described embodiment 1-3 is tailored into the platelet of standard, then uses oxygen index measurer HC-2(Nanjing
Jiangning District analytical tool factory) and analytical tool factory of horizontal vertical burning analyzer CZF-3(Jiangning county) respectively to fire-retardant
Wood-plastic material carries out oxygen index (OI) and combustibility measures, oxygen index (OI) 33%-36%, and horizontal vertical combustibility is without catching fire, and cigarette is light,
Flame retardant effect is good.
(2) Mechanics Performance Testing experiment
Sample prepared by above-described embodiment 1-3 tailors growth 115mm, wide 10mm, the standard platelet of thick 2.5mm, then uses
Tester for elongation 5585(American I NSTRON) and impact specimen machine ZBC1251-B(Mei Tesi industrial system company) respectively to resistance
Firebrand moulding material carries out stretching and impact test, tensile figure (maximum pull, unit: N) 325.6-357.4, Impact Index
(toughness, non-notch), unit: ki/m2,4.513-5.672, note: draw speed is 2mm/min.
In sum, the Wood-plastic material good flame retardation effect of the present invention, strong shock resistance, toughness is strong, has both obtained excellent
Fire resistance maintain again the preferable mechanical property of Wood-plastic material, be the excellent flame-retardant wood-plastic material of a kind of performance, can promote should
With, there is significant economic and social benefit.
Above content it cannot be assumed that the present invention be embodied as be confined to these explanation, technology belonging to the present invention is led
For the those of ordinary skill in territory, without departing from the inventive concept of the premise, it is also possible to make some simple deduction or replace,
All should be considered as belonging to the scope of patent protection that the present invention is determined by the claims submitted to.
Claims (10)
1. a flame-retardant wood-plastic material, it is characterised in that in units of weight portion, including following raw material: mulberry wood powder 30-60
Part, corn stalk powder 20-40 part, old and useless newspaper powder 8-12 part, waste and old packaging bag plastic pellet 6-10 part, filler 6-8 part, synthesis
Agent 4-6 part, lubricant 1-2 part, antimildew and antibacterial agent 1-2 part, hygroscopic agent 1-2 part, fire retardant 2-4 part, smoke suppressant 2-4 part, bonding
Agent 6-10 part;
Described filler is Kaolin;
Described synthetics is in units of weight portion, including following raw material: propellant 0.3-0.5 part, coupling agent 0.6-0.8 part, phase
Hold agent 0.4-0.6 part, antioxidant 0.3-0.5 part, regulator 0.3-0.6 part, hardening agent 0.3-0.5 part, flocculation agent 0.6-0.8
Part, plasticizer 0.6-0.9 part, stabilizer 0.3-0.4 part, terminator 0.3-0.4 part;
Described hardening agent is in units of weight portion, including following raw material: styrene 0.08-0.12 part, methylcrotonic acid methyl ester
0.08-0.12 part, vinylacetate 0.06-0.1 part, cobalt naphthenate 0.04-0.08 part, zinc chloride 0.04-0.08 part;
Described stabilizer is organic tin stabilizer;
Described lubricant is maleic anhydride grafted polyethylene wax;
Described antimildew and antibacterial agent is antimildew and antibacterial agent AEM5700-B;
Described hygroscopic agent is silica gel;
Described fire retardant is in units of weight portion, including following raw material: antimony oxide 0.4-0.8 part, chlordene cyclododecane
0.2-0.5 part, 2-chloroethyl-2-bromoethyl carboxylate 0.2-0.5 part, molybdenum oxide 0.4-0.7 part, Lauxite 0.2-0.5 part,
POLYPROPYLENE GLYCOL 0.2-0.4 part, bentonite 0.4-0.6 part;
Described smoke suppressant is in units of weight portion, including following raw material: dibutyl tin laurate 0.6-1.2 part, zirconium hydroxide
0.6-1.2 part, Pulvis Talci 0.4-0.8 part, ferrum oxide 0.4-0.8 part;
Described binding agent, with tapioca as raw material, carries out cross-linked graft reaction, then by elder generation with triglyceride, percarbamide
Carry out cross-linking reaction with potassium hydroxide and epoxychloropropane, then carry out pre-gelatinized reaction, be finally dried, pulverize, sieve and obtain;
The preparation method of described flame-retardant wood-plastic material, comprises the following steps:
S1: prepare synthetics, the preparation method of described synthetics, comprise the following steps:
S11: propellant, coupling agent, compatilizer, antioxidant mixing are warming up to 115-125 DEG C, are 100-300r/ at rotating speed
React 40-90 min under min, prepare material A;
S12: be warming up to 145-155 DEG C after adding regulator, hardening agent, flocculation agent mixing in the material A that step S11 prepares,
Under rotating speed is 300-400r/min, reacts 150-220 min, prepares material B;
S13: be cooled to 115-120 DEG C after adding plasticizer, stabilizer, terminator mixing in the material B that step S12 prepares,
Under rotating speed is 200-300r/min, reacts 60-100 min, prepares synthetics;
S2: prepare binding agent, the preparation method of described binding agent, comprise the following steps:
S21: compound concentration is para arrowroot slurry A of 20-23Be ';
S22: it is 1.5%-1.8% triglyceride, percarbamide that para arrowroot slurry A in step S21 adds concentration, then in temperature
Degree is for 26-34 DEG C, and speed of agitator is to carry out cross-linked graft reaction 0.6-1h under 50-80r/min, prepares slurry B;
S23: adding potassium hydroxide and epoxychloropropane in the slurry B of step S22, be then 32-36 DEG C in temperature, stirring turns
Speed, for carrying out cross-linking reaction 0.2-0.5h under 60-100r/min, prepares slurry C;
S24: be delivered to the slurry C of step S23 in cylindrical drier carry out pre-gelatinized and do at temperature is 140-145 DEG C
Dry, prepare the material D of water content≤6%;
S25: wind after the material D pulverizing of step S24, excessively 60-100 mesh sieve is delivered to whirlwind separator and is collected, prepare viscous
Mixture;
S3: by step S1 prepare synthetics, step S2 prepare binding agent, mulberry wood powder, corn stalk powder, old and useless newspaper
Powder, waste and old packaging bag plastic pellet, filler, lubricant, antimildew and antibacterial agent, hygroscopic agent, fire retardant, smoke suppressant put into pressure cooker
In, HIGH PRESSURE TREATMENT 0.5-0.8h under pressure is 12-15MPa, prepare raw material A;
S4: the raw material A that step S3 prepares is put into freezing 2-4h at temperature≤-30 DEG C, prepares raw material B;
S5: put in dehydrator by the raw material B that step S4 prepares, dries to water content≤5%, system at temperature is 78-80 DEG C
Obtain raw material C;
S6: raw material C step S5 prepared puts in blender, stirs 6-9min under rotating speed is 300-500r/min, prepares
Particle;
S7: put in extruder by the particle that step S6 prepares, extrudes at temperature is 185-190 DEG C, through cooling molding,
Prepare flame-retardant wood-plastic material.
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that propellant described in step S11 is aerosol
Propellant.
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that coupling agent described in step S11 is furfural.
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that compatilizer described in step S11 is acrylic acid
Type compatilizer.
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that antioxidant described in step S11 is
WINGSTAYL。
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that regulator described in step S12 is
JINHASS。
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that flocculation agent described in step S12 is polymerization chlorine
Change aluminum.
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that plasticizer described in step S13 is citric acid
Ester.
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that terminator described in step S13 is styrene.
Flame-retardant wood-plastic material the most according to claim 1, it is characterised in that cool down the mixing of employing described in step S7
Liquid is to be that 95-100:4-6:2-3 makes by water, ethanol, the mass ratio of ethyl salicylate.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109021394A (en) * | 2018-07-13 | 2018-12-18 | 安徽钰锦生态木材料有限公司 | A kind of Wood-plastic material and preparation method thereof with flame retarding function |
CN109251546A (en) * | 2018-07-13 | 2019-01-22 | 安徽钰锦生态木材料有限公司 | A kind of economic and environment-friendly type Wood-plastic material and preparation method thereof |
CN114573995A (en) * | 2022-03-12 | 2022-06-03 | 昆明理工大学 | Preparation method of elastic buffer body taking corn stalks as biological templates |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1857884A (en) * | 2006-06-02 | 2006-11-08 | 河北华龙机械有限公司 | Wood-plastic composite material and production process of composite material plate |
CN1944501A (en) * | 2006-10-31 | 2007-04-11 | 云南华威废弃物资源化有限公司 | Composite material made of waste material and its preparing method |
CN101138857A (en) * | 2007-10-23 | 2008-03-12 | 孔繁诚 | Wood plastic plank stuff production technology and equipment thereof |
CN105647214A (en) * | 2016-01-29 | 2016-06-08 | 安徽以诺木塑板材科技有限公司 | Flame-retardant type wood-plastic material |
CN105685113A (en) * | 2016-03-25 | 2016-06-22 | 庞用 | Preparation method of novel environment-friendly mosquito-repellent incense |
CN105694502A (en) * | 2016-01-29 | 2016-06-22 | 安徽以诺木塑板材科技有限公司 | Environment-friendly wood-plastic material |
-
2016
- 2016-07-12 CN CN201610545112.4A patent/CN106189301A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1857884A (en) * | 2006-06-02 | 2006-11-08 | 河北华龙机械有限公司 | Wood-plastic composite material and production process of composite material plate |
CN1944501A (en) * | 2006-10-31 | 2007-04-11 | 云南华威废弃物资源化有限公司 | Composite material made of waste material and its preparing method |
CN101138857A (en) * | 2007-10-23 | 2008-03-12 | 孔繁诚 | Wood plastic plank stuff production technology and equipment thereof |
CN105647214A (en) * | 2016-01-29 | 2016-06-08 | 安徽以诺木塑板材科技有限公司 | Flame-retardant type wood-plastic material |
CN105694502A (en) * | 2016-01-29 | 2016-06-22 | 安徽以诺木塑板材科技有限公司 | Environment-friendly wood-plastic material |
CN105685113A (en) * | 2016-03-25 | 2016-06-22 | 庞用 | Preparation method of novel environment-friendly mosquito-repellent incense |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109021394A (en) * | 2018-07-13 | 2018-12-18 | 安徽钰锦生态木材料有限公司 | A kind of Wood-plastic material and preparation method thereof with flame retarding function |
CN109251546A (en) * | 2018-07-13 | 2019-01-22 | 安徽钰锦生态木材料有限公司 | A kind of economic and environment-friendly type Wood-plastic material and preparation method thereof |
CN114573995A (en) * | 2022-03-12 | 2022-06-03 | 昆明理工大学 | Preparation method of elastic buffer body taking corn stalks as biological templates |
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