CN110359281A - A kind of fire-retardant rapid-curing cutback glue and preparation method thereof - Google Patents
A kind of fire-retardant rapid-curing cutback glue and preparation method thereof Download PDFInfo
- Publication number
- CN110359281A CN110359281A CN201910729398.5A CN201910729398A CN110359281A CN 110359281 A CN110359281 A CN 110359281A CN 201910729398 A CN201910729398 A CN 201910729398A CN 110359281 A CN110359281 A CN 110359281A
- Authority
- CN
- China
- Prior art keywords
- retardant
- fire
- rapid
- curing cutback
- flame retardant
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/236—Esters of carboxylic acids; Esters of carbonic acid containing halogen atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/579—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them modified by compounds containing phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Abstract
The invention discloses a kind of fire-retardant rapid-curing cutback glue and preparation method thereof, fire-retardant rapid-curing cutback glue is grouped as by the group of following mass fraction: 4-20% phosphorus, nitrogen compound based flame retardant, 10-30% inorganic compound based flame retardant, 60-80% Polyvinyl acetate adhesive 1.5-3.5% carbon black, 3-5% water, magnalium hydrotalcite can be used as gas phase fire retardant in component, and generation carbon dioxide is fire-retardant and foams to other high molecular fire retardant components, and polysiloxanes fire retardant has good high-temperature stability and anti-flammability.Organophosphorus-type aqueous polyurethane, nitrogenous acrylate monomer can be formed by curing one layer of fine and close fire prevention cured film in substrate surface, and macromolecule carbon fire retardant has both the double effects of carbon source and gas source, and the expansion type flame retardant as coating uses.Macromolecule carbon fire retardant can form fine and close high quality foamed char in substrate surface, be covered on the transmission of substrate surface starvation and heat to achieve the purpose that protect substrate.
Description
Technical field
The present invention relates to flame retardant coating preparation field, in particular to a kind of fire-retardant rapid-curing cutback glue and preparation method thereof.
Background technique
As follows for the fire-retardant principle of fire-retardant fireproof coating: (1) fire-retardant fireproof coating itself has fire retardant or noninflammability, base
Material not direct contacted with air and delay substrate ignition；(2) fire-retardant fireproof coating meets fiery be heated and decomposites non-flammable gases,
The inflammable gas and oxygen concentration of surrounding are watered down, burning is inhibited；(3) fire-retardant fireproof coating heat, which can generate, slows down or terminates burning
The free radical of chain reaction；(4) fire-retardant fireproof coating meets fire or heated foaming and intumescing, forms fine and close and uniform spongy or bee
The fine and close carbonaceous froth bed of nest shape can delay heat to propagate to substrate, avoid the ablation of flame and high temperature to substrate.
High molecular fire retardant material is mostly used to be prepared in fire-retardant fireproof coating at present, usually, the fire-retardant machine of condensed phase
Reason and gas phase fire retardant mechanism are the main fire retardant mechanisms of high molecular fire retardant material.Condensed phase fire retardant mechanism refers in polymer heat
Shi Shengcheng Protective isolation layer of charcoal is to inhibit the heat exchange and quality (pyrolysis product and oxygen between high molecular material and the external world
Gas) it shifts and then realizes fire-retardant.Some layer of charcoal such as honeycomb layer of charcoal also has the function of capturing free radical.Gas phase fire retardant mechanism is
Refer to that polymer heat discharges a large amount of non-flammable compressive gas substance to take away heat, dilution oxygen and imflammable gas concentration, even
Flame blow-off is fire-retardant to realize.Other than two above mechanism, many new fire retardant mechanisms are proposed, are such as based on certain
The novel flame-retardant mechanism etc. of a little physical principles.Those high molecular materials for containing numerous ignition-proof elements and flame retarding construction are come
It says, fire retardant mechanism needs in the light of actual conditions to be analyzed.In fact, the burning of high molecular material with it is fire-retardant be sufficiently complex
Process, different fire retardant mechanisms be also can not completely and point, the fire-retardant realization of high molecular material is usually a variety of fire-retardant machines
Manage coefficient result.
Summary of the invention
The technical problems to be solved by the invention: the present invention provides a kind of fire-retardant rapid-curing cutback glue and preparation method thereof, can be same
When enhance the flame retardant effects of the fabric carriers such as felt by the fire-retardant gentle mutually fire-retardant two kinds of fire-retardant modes of condensed phase.
In order to solve the above technical problems, the present invention provides technical solution below:
A kind of fire-retardant rapid-curing cutback glue, is grouped as by the group of following mass fraction:
4-20% phosphorus, nitrogen compound based flame retardant, 10-30% inorganic compound based flame retardant, 60-80% polyvinyl acetate
Adhesive 1.5-3.5% carbon black, 3-5% water；The Polyvinyl acetate adhesive is quick-dry type, the degree of polymerization 540.
Preferably, the inorganic compound based flame retardant is magnalium hydrotalcite and/or macromolecule carbon fire retardant.
Preferably, the macromolecule carbon fire retardant is prepared as follows acquisition:
(1) under the continuous stirring condition of 140 DEG C of temperature and 500r/min, by 8.8g EDTA in 250mL three-neck flask
It is dissolved in 100mL DMSO；
(2) then, 3.5g N, N'- dicyclohexylcarbodiimide, after stirring 1h, by 5.5g melamine are added into solution
Amine and 2.0g 4-dimethylaminopyridine are added in flask；
(3) said mixture reacts for 24 hours at 140 DEG C, then obtains product by filtering, then repeat to rush with deionized water
It washes, for 24 hours, finally obtaining faint yellow solid is macromolecule carbon fire retardant for drying in 80 DEG C of baking oven.
Preferably, the phosphorus, nitrogen compound based flame retardant by organophosphorus-type aqueous polyurethane, nitrogenous acrylate monomer,
One of polysiloxanes fire retardant or a variety of compositions.
Preferably, the nitrogenous acrylate monomer synthesizes as follows is made:
Three epoxies third of 0.lmol are added in the 250mL three-necked flask that thermometer, dropping funel, reflux condensing tube are housed
Base chlorinated isocyanurates, the acrylic acid of 0.3mol, 100mL Isosorbide-5-Nitrae-dioxane, the triethylamine of 0.3mL are added as catalyst
The p-hydroxyanisole of 0.3g is warming up to 105 DEG C as polymerization inhibitor, reaction, and reacts 2.5 hours at this temperature, then rotates
Unreacted reagent and solvent are removed, obtaining sticky transparency liquid is nitrogenous acrylate monomer.
Preferably, the polysiloxanes fire retardant is made as follows:
(A) by 60mL toluene, 7mL polymethyl hydrogen siloxane is added to containing stirrer, thermometer and reflux condensing tube
In flask；When being heated to 70 DEG C, the catalyst of final concentration 80ppm is added, is passed through nitrogen, mixture is stirred at such a temperature
15min is warming up to 100 DEG C with activated catalyst later；The method for preparing catalyst is as follows: 1.5g chloroplatinic acid being taken to be placed in _ 70g
In pretreated isopropanol, it is protected from light after dissolution is sufficiently stirred and obtains transparent orange-yellow liquid, it is spare to be protected from light storage；
(B) toluene solution of 25mL triethoxysilane containing isocyanatopropyl in constant pressure funnel is at the uniform velocity added drop-wise in 3h
In flask, after sustained response 10h, the toluene solution in 1.5h by 40mL in constant pressure funnel containing allyl glycidyl ether is at the uniform velocity
It is added drop-wise in flask, isothermal reaction 8h；The molar ratio of the isocyanatopropyl triethoxysilane and allyl glycidyl ether
For 2:5；
(C) intermediate is just obtained by revolving removal solvent and extra raw material, later by intermediate, 9,10- dihydros-
9- oxa- -10- phospho hetero phenanthrene -10- oxide, the triphenylphosphine of 0.28wt% and the toluene of 150mL rectifying are added to containing stirring
It mixes in the flask under the inert atmosphere of son, thermometer and reflux condensing tube, is warming up to 100 DEG C, reacts knot after isothermal reaction 12h
Beam removes solvent by revolving；
(D) powder of acquisition is repeatedly washed with dehydrated alcohol and removes the extra miscellaneous -10- phospha of 9,10- dihydro-9-oxy
Phenanthrene -10- oxide is repeatedly washed with deionized water, and the solid powder that suction filtration obtains is set to dry 15h in 90 DEG C of baking oven later
Up to polysiloxanes fire retardant.
A kind of preparation method of above-mentioned fire-retardant rapid-curing cutback glue is prepared by following specific steps:
(1) 3 ton of blender, setting speed≤85,30-80 DEG C of heating temperature；
(2) feed intake inorganic compound based flame retardant 10-30wt%, Polyvinyl acetate adhesive 60-80wt%；
(3) feed intake phosphorus, nitrogen compound based flame retardant 4-20wt%；
(4) feed intake water 3-5wt%, carbon black 1.5-3.5wt%；
(5) stirring 1-1.5 hours after the completion of feeding intake, shut down 1-1.5 hours, and booting runs uniform stirring 2-3 hours to obtain the final product.
It is that the present invention obtains the utility model has the advantages that
1, magnalium hydrotalcite can be used as gas phase fire retardant, decomposes in burning and generates a large amount of carbon dioxide gas and water,
Carbon dioxide can prevent to burn again, reduce oxygen concentration, a large amount of carbon dioxide again can be to phosphorus, nitrogen compound based flame retardant and height
Molecular carbon fire retardant foams, and further carries out to the substrate being coated or impregnated with fire-retardant.
2, polysiloxanes fire retardant-[Si-O]xThe Gao Jian of significant flexibility and-Si-O- key forces polysiloxanes to have
There is good high-temperature stability.The low surface tension of silicon keeps its heat Shi Yixiang matrix surface mobile and forms two in matrix surface
Silicon oxide layer, this layer of silica can reduce heat transfer and inhibit the release of fuel gas therefore inhibit polymer into one
Step degradation.
3, organophosphorus-type aqueous polyurethane, nitrogenous acrylate monomer are then carried out by the fire-retardant mode of condensed phase fire-retardant,
Organophosphorus-type aqueous polyurethane, nitrogenous acrylate monomer can be formed by curing one layer of fine and close fire prevention cured film in substrate surface,
Cured film thermal stability with higher and flame retardant property.
4, macromolecule carbon fire retardant obtains flexibility while improving coating adhesion.With melamine and ethylenediamine tetraacetic
Acetic acid is that the macromolecule carbon fire retardant of Material synthesis has both the double effects of carbon source and gas source, the expansion type flame retardant as coating
It uses.Intramolecular dehydration and intermolecular de- can occur in thermal histories for a large amount of carboxyl end groups contained in macromolecule carbon fire retardant
Water, to realize the crosslinking of carbon residue.Crosslinking carbon residue interacts to form the high quality foamed char of surface compact, is covered on substrate
The transmission of surface starvation and heat is to achieve the purpose that protect substrate.
Specific embodiment
Below by the description to embodiment, specific embodiments of the present invention will be described in further detail, with side
Those skilled in the art is helped to have more complete, accurate and deep understanding to inventive concept of the invention, technical solution.
Embodiment 1: it is prepared as follows fire-retardant rapid-curing cutback glue:
One, the preparation of raw material and prefabricated:
Polyvinyl acetate adhesive is quick-dry type, the degree of polymerization 540.
Inorganic compound based flame retardant is macromolecule carbon fire retardant, the preparation method is as follows:
(1) under the continuous stirring condition of 140 DEG C of temperature and 500r/min, by 8.8g EDTA in 250mL three-neck flask
It is dissolved in 100mL DMSO；
(2) then, 3.5g N, N'- dicyclohexylcarbodiimide, after stirring 1h, by 5.5g melamine are added into solution
Amine and 2.0g 4-dimethylaminopyridine are added in flask；
(3) said mixture reacts for 24 hours at 140 DEG C, then obtains product by filtering, then repeat to rush with deionized water
It washes, for 24 hours, finally obtaining faint yellow solid is macromolecule carbon fire retardant for drying in 80 DEG C of baking oven.
Nitrogenous acrylate monomer synthesizes as follows to be made:
Three epoxies third of 0.lmol are added in the 250mL three-necked flask that thermometer, dropping funel, reflux condensing tube are housed
Base chlorinated isocyanurates, the acrylic acid of 0.3mol, 100mL Isosorbide-5-Nitrae-dioxane, the triethylamine of 0.3mL are added as catalyst
The p-hydroxyanisole of 0.3g is warming up to 105 DEG C as polymerization inhibitor, reaction, and reacts 2.5 hours at this temperature, then rotates
Unreacted reagent and solvent are removed, obtaining sticky transparency liquid is nitrogenous acrylate monomer.
Polysiloxanes fire retardant is made as follows:
(A) by 60mL toluene, 7mL polymethyl hydrogen siloxane is added to containing stirrer, thermometer and reflux condensing tube
In flask；When being heated to 70 DEG C, the catalyst of final concentration 80ppm is added, is passed through nitrogen, mixture is stirred at such a temperature
15min is warming up to 100 DEG C with activated catalyst later；The method for preparing catalyst is as follows: 1.5g chloroplatinic acid being taken to be placed in _ 70g
In pretreated isopropanol, it is protected from light after dissolution is sufficiently stirred and obtains transparent orange-yellow liquid, it is spare to be protected from light storage；
(B) toluene solution of 25mL triethoxysilane containing isocyanatopropyl in constant pressure funnel is at the uniform velocity added drop-wise in 3h
In flask, after sustained response 10h, the toluene solution in 1.5h by 40mL in constant pressure funnel containing allyl glycidyl ether is at the uniform velocity
It is added drop-wise in flask, isothermal reaction 8h；The molar ratio of the isocyanatopropyl triethoxysilane and allyl glycidyl ether
For 2:5；
(C) intermediate is just obtained by revolving removal solvent and extra raw material, later by intermediate, 9,10- dihydros-
9- oxa- -10- phospho hetero phenanthrene -10- oxide, the triphenylphosphine of 0.28wt% and the toluene of 150mL rectifying are added to containing stirring
It mixes in the flask under the inert atmosphere of son, thermometer and reflux condensing tube, is warming up to 100 DEG C, reacts knot after isothermal reaction 12h
Beam removes solvent by revolving；
(D) powder of acquisition is repeatedly washed with dehydrated alcohol and removes the extra miscellaneous -10- phospha of 9,10- dihydro-9-oxy
Phenanthrene -10- oxide is repeatedly washed with deionized water, and the solid powder that suction filtration obtains is set to dry 15h in 90 DEG C of baking oven later
Up to polysiloxanes fire retardant.
Phosphorus, nitrogen compound based flame retardant by nitrogenous acrylate monomer, polysiloxanes fire retardant by weight 1:1 prepare and
At.
Two, the preparation of fire-retardant rapid-curing cutback glue:
(1) 3 ton of blender, setting speed≤85,30 DEG C of heating temperature；
(2) feed intake inorganic compound based flame retardant 10wt%, Polyvinyl acetate adhesive 80wt%；
(3) feed intake phosphorus, nitrogen compound based flame retardant 5.5wt%；
(4) feed intake water 3wt%, carbon black 1.5wt%；
(5) stirring 1 hour after the completion of feeding intake, shuts down 1 hour, and booting runs uniform stirring 2 hours to obtain the final product.
Embodiment 2: it is prepared as follows fire-retardant rapid-curing cutback glue:
One, the preparation of raw material and prefabricated:
Polyvinyl acetate adhesive is quick-dry type, the degree of polymerization 600.
Inorganic compound based flame retardant is magnalium hydrotalcite, crosses 150 mesh screens after magnalium hydrotalcite grinding to obtain the final product.
Nitrogenous acrylate monomer, polysiloxanes fire retardant are same as Example 1.
Phosphorus, nitrogen compound based flame retardant are fire-retardant by organophosphorus-type aqueous polyurethane, nitrogenous acrylate monomer, polysiloxanes
Agent is prepared by weight 1:2:4.
Two, the preparation of fire-retardant rapid-curing cutback glue:
(1) 3 ton of blender, setting speed≤85,80 DEG C of heating temperature；
(2) feed intake inorganic compound based flame retardant 30wt%, Polyvinyl acetate adhesive 60wt%；
(3) feed intake phosphorus, nitrogen compound based flame retardant 4wt%；
(4) feed intake water 4wt%, carbon black 2wt%；
(5) stirring 1.5 hours after the completion of feeding intake, shut down 1.5 hours, and booting runs uniform stirring 3 hours to obtain the final product.
Embodiment 3: it is prepared as follows fire-retardant rapid-curing cutback glue:
One, the preparation of raw material and prefabricated:
Polyvinyl acetate adhesive is quick-dry type, the degree of polymerization 400.
Inorganic compound based flame retardant is that magnalium hydrotalcite and macromolecule carbon fire retardant proportion are made, magnalium hydrotalcite and height
The mass ratio of molecular carbon fire retardant is 1:3.
Magnalium hydrotalcite, macromolecule carbon fire retardant, polysiloxanes fire retardant are same as Example 2.
Phosphorus, nitrogen compound based flame retardant are polysiloxanes fire retardant.
Two, the preparation of fire-retardant rapid-curing cutback glue:
(1) 3 ton of blender, setting speed≤85,55 DEG C of heating temperature；
(2) feed intake inorganic compound based flame retardant 20wt%, Polyvinyl acetate adhesive 67.5wt%；
(3) feed intake phosphorus, nitrogen compound based flame retardant 4wt%；
(4) feed intake water 5wt%, carbon black 3.5wt%；
(5) stirring 1 hour after the completion of feeding intake, shuts down 1.5 hours, and booting runs uniform stirring 2.5 hours to obtain the final product.
Embodiment 4: it is prepared as follows fire-retardant rapid-curing cutback glue:
One, the preparation of raw material and prefabricated:
Polyvinyl acetate adhesive is quick-dry type, the degree of polymerization 300.
Inorganic compound based flame retardant is that magnalium hydrotalcite and macromolecule carbon fire retardant proportion are made, magnalium hydrotalcite and height
The mass ratio of molecular carbon fire retardant is 1:4.
Magnalium hydrotalcite, macromolecule carbon fire retardant are that nitrogenous acrylate monomer is same as Example 2.
Phosphorus, nitrogen compound based flame retardant are nitrogenous acrylate monomer.
Two, the preparation of fire-retardant rapid-curing cutback glue:
(1) 3 ton of blender, setting speed≤85,65 DEG C of heating temperature；
(2) feed intake inorganic compound based flame retardant 12wt%, Polyvinyl acetate adhesive 62.5wt%；
(3) feed intake phosphorus, nitrogen compound based flame retardant 20wt%；
(4) feed intake water 3wt%, carbon black 2.5wt%；
(5) stirring 1.5 hours after the completion of feeding intake, shut down 1 hour, and booting runs uniform stirring 2.5 hours to obtain the final product.
Comparative examples: preparing a kind of novel flame-retardant glue according to method disclosed in Chinese patent CN109161365A,
For subsequent fire-retardant experiment contrast.
In order to test performance of the invention, tested as follows:
1, flame retardant property is tested
The novel flame-retardant glue prepared in the fire-retardant rapid-curing cutback glue and comparative examples that prepare in Examples 1 to 4 is distinguished
Felt is impregnated, dipping takes out afterwards for 24 hours, is used as test specimen after drying under 55 degrees Celsius, carries out following flame retardant property
Test:
1.1 limit oxygen index test (LOI)
According to ASTMD 2863-10, measuring limit oxygen index (OI) (LOI) value, sample size on digital oxygen index (OI) meter ZR-01
For 80 × 10 × 4mm.
1.2 vertical burn tests (UL-94)
It is tested using JR-SSC-A type horizontal vertical combustion instrument (Shenyang crape myrtle mechanical & electronic equipment corporation, Ltd), with ASTM
D3801-10 is standard, batten size: 130mm × 13mm × 1.6mm.
Flame test result is shown in Table 1:
1 flame test result of table
Table 1 is the result shows that be remarkably improved the LOI and UL-94 of substrate, the higher theory of LOI value after present invention dipping felt substrate
The flame retardant effect of bright material is better, and V0 flame retardant effect is best in UL-94 classification, and the flame retardant effect of V1~2 is gradually deteriorated.
2, cohesive force test (3M adhesive tape test)
The novel flame-retardant glue prepared in the fire-retardant rapid-curing cutback glue and comparative examples that prepare in Examples 1 to 4 is distinguished
It is uniformly painted on the plastic plate of PP material, brushing amount is 150g/m2It is used as sample after natural drying.According to ASTM D 3359-
09 carries out the adhesion test of the coating on sample.Cutting tool be equipped with include between be divided into 1.0mm 5 teeth blade.
Cross-cut pattern is formed at about 1 inch using cutting tool.Intersecting angle is 90 °.By 3M tape-stripping to cutting surfaces
And ensure to contact with the good of coating, it then moves back and removes in 90s.It shares 3M adhesive tape bonding 5 times, by observing plastic sheet surface institute
Surplus coating grid number characterizes coating to the adhesive force of substrate to be classified, and 0 grade of adhesive force is best, and 5 grades of adhesive force are worst.Bonding
The region that power test carries out shares 3, and test zone is located at the same face of same sample and is not overlapped mutually.
The attachment grade of the fire-retardant rapid-curing cutback glue of table 2 measures
| Group | Region 1 | Region 2 | Region 3 |
| Embodiment 1 | 1 | 0~1 | 0 |
| Embodiment 2 | 0 | 0 | 1 |
| Embodiment 3 | 0 | 0 | 0 |
| Embodiment 4 | 0 | 1 | 0 |
| Comparative examples | 5 | 4 | 5 |
Table 2 the result shows that, the present invention can be bonded in the smooth PP substrate surface in surface well, attached in smooth substrate
Put forth effort to be significantly higher than comparative examples, can be applied to the fire protection flame retarding of a variety of substrate surfaces or inside.
In conclusion magnalium hydrotalcite can be used as gas phase fire retardant, is decomposed in burning and generate a large amount of carbon dioxide gas
Body and water, carbon dioxide can prevent to burn again, reduce oxygen concentration, and a large amount of carbon dioxide can hinder phosphorus, nitrification species again
Combustion agent and macromolecule carbon fire retardant foam, and further carry out to the substrate being coated or impregnated with fire-retardant.Polysiloxanes fire retardant-
[Si-O]xThe Gao Jian of significant flexibility and-Si-O- key forces polysiloxanes to have good high-temperature stability.Silicon it is low
Surface tension keeps its heat Shi Yixiang matrix surface mobile and forms silicon dioxide layer in matrix surface, this layer of silica can be with
It reduces heat transfer and inhibits the release of fuel gas therefore inhibit the further degradation of polymer.The aqueous poly- ammonia of organophosphorus-type
Ester, nitrogenous acrylate monomer then carry out fire-retardant, organophosphorus-type aqueous polyurethane, nitrogenous propylene by the fire-retardant mode of condensed phase
Acid ester monomer can be formed by curing one layer of fine and close fire prevention cured film, cured film thermal stability with higher and resistance in substrate surface
Fire performance.Macromolecule carbon fire retardant obtains flexibility while improving coating adhesion.With melamine and ethylenediamine tetrem
Acid is that the macromolecule carbon fire retardant of Material synthesis has both the double effects of carbon source and gas source, and the expansion type flame retardant as coating makes
With.Intramolecular dehydration and intermolecular de- can occur in thermal histories for a large amount of carboxyl end groups contained in macromolecule carbon fire retardant
Water, to realize the crosslinking of carbon residue.Crosslinking carbon residue interacts to form the high quality foamed char of surface compact, is covered on substrate
The transmission of surface starvation and heat is to achieve the purpose that protect substrate.
The above examples only illustrate the technical idea of the present invention, and this does not limit the scope of protection of the present invention, all
According to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within the scope of the present invention
Within；The technology that the present invention is not directed to can be realized by the prior art.
Claims (7)
1. a kind of fire-retardant rapid-curing cutback glue, which is characterized in that be grouped as by the group of following mass fraction:
4-20% phosphorus, nitrogen compound based flame retardant, 10-30% inorganic compound based flame retardant, 60-80% polyvinyl acetate gluing
Agent 1.5-3.5% carbon black, 3-5% water；The Polyvinyl acetate adhesive is quick-dry type, the degree of polymerization 540.
2. a kind of fire-retardant rapid-curing cutback glue according to claim 1, it is characterised in that: the inorganic compound based flame retardant
For magnalium hydrotalcite and/or macromolecule carbon fire retardant.
3. a kind of fire-retardant rapid-curing cutback glue according to claim 2, it is characterised in that: the macromolecule carbon fire retardant is by such as
Lower section method prepares:
(1) under the continuous stirring condition of 140 DEG C of temperature and 500r/min, 8.8g EDTA is dissolved in 250mL three-neck flask
In 100mL DMSO；
(2) then, be added 3.5g N into solution, N'- dicyclohexylcarbodiimide, after stirring 1h, by 5.5g melamine and
2.0g 4-dimethylaminopyridine is added in flask；
(3) said mixture reacts for 24 hours at 140 DEG C, then obtains product by filtering, then repeat to rinse with deionized water,
For 24 hours, finally obtaining faint yellow solid is macromolecule carbon fire retardant for drying in 80 DEG C of baking oven.
4. a kind of fire-retardant rapid-curing cutback glue according to claim 1, it is characterised in that: the phosphorus, nitrification species are fire-retardant
Agent is by one of organophosphorus-type aqueous polyurethane, nitrogenous acrylate monomer, polysiloxanes fire retardant or a variety of forms.
5. a kind of fire-retardant rapid-curing cutback glue according to claim 4, it is characterised in that: the nitrogenous acrylate monomer is pressed
Following method synthesis is made:
Three glycidyl that 0.lmol is added in the 250mL three-necked flask that thermometer, dropping funel, reflux condensing tube are housed are different
Cyanurate, the acrylic acid of 0.3mol, 100mL Isosorbide-5-Nitrae-dioxane, the triethylamine of 0.3mL are added 0.3g's as catalyst
P-hydroxyanisole is warming up to 105 DEG C as polymerization inhibitor, reaction, and reacts at this temperature 2.5 hours, and then rotation removes not
The reagent and solvent of reaction, obtaining sticky transparency liquid is nitrogenous acrylate monomer.
6. a kind of fire-retardant rapid-curing cutback glue according to claim 4, it is characterised in that: the polysiloxanes fire retardant is by such as
Lower section method is made:
(A) by 60mL toluene, 7mL polymethyl hydrogen siloxane is added to the flask containing stirrer, thermometer and reflux condensing tube
In；When being heated to 70 DEG C, the catalyst of final concentration 80ppm is added, is passed through nitrogen, mixture is stirred into 15min at such a temperature
With activated catalyst, it is warming up to 100 DEG C later；The method for preparing catalyst is as follows: take 1.5g chloroplatinic acid be placed in _ 70g locates in advance
In isopropanol after reason, it is protected from light after dissolution is sufficiently stirred and obtains transparent orange-yellow liquid, it is spare to be protected from light storage；
(B) toluene solution of 25mL triethoxysilane containing isocyanatopropyl in constant pressure funnel is at the uniform velocity added drop-wise to flask in 3h
In, after sustained response 10h, the toluene solution in 1.5h by 40mL in constant pressure funnel containing allyl glycidyl ether is at the uniform velocity added dropwise
Into flask, isothermal reaction 8h；The molar ratio of the isocyanatopropyl triethoxysilane and allyl glycidyl ether is 2:
5；
(C) intermediate is just obtained by revolving removal solvent and extra raw material, later by intermediate, 9,10- dihydro-9-oxies
Miscellaneous -10- phospho hetero phenanthrene -10- oxide, the triphenylphosphine of 0.28wt% and the toluene of 150mL rectifying be added to containing stirrer,
In flask under the inert atmosphere of thermometer and reflux condensing tube, 100 DEG C are warming up to, reacting after isothermal reaction 12h terminates, and passes through
Revolving removal solvent；
(D) powder of acquisition is repeatedly washed with dehydrated alcohol and removes the extra miscellaneous -10- phospho hetero phenanthrene -10- of 9,10- dihydro-9-oxy
Oxide is repeatedly washed with deionized water, and it is to obtain the final product poly- that the solid powder that suction filtration obtains is set to dry 15h in 90 DEG C of baking oven later
Siloxane flame retardant.
7. a kind of preparation method of rapid-curing cutback glue fire-retardant as described in any one of claim 1-6, which is characterized in that by following tool
The preparation of body step:
(1) 3 ton of blender, setting speed≤85,30-80 DEG C of heating temperature；
(2) feed intake inorganic compound based flame retardant 10-30wt%, Polyvinyl acetate adhesive 60-80wt%；
(3) feed intake phosphorus, nitrogen compound based flame retardant 4-20wt%；
(4) feed intake water 3-5wt%, carbon black 1.5-3.5wt%；
(5) stirring 1-1.5 hours after the completion of feeding intake, shut down 1-1.5 hours, and booting runs uniform stirring 2-3 hours to obtain the final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910729398.5A CN110359281A (en) | 2019-08-08 | 2019-08-08 | A kind of fire-retardant rapid-curing cutback glue and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910729398.5A CN110359281A (en) | 2019-08-08 | 2019-08-08 | A kind of fire-retardant rapid-curing cutback glue and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110359281A true CN110359281A (en) | 2019-10-22 |
Family
ID=68223401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910729398.5A Pending CN110359281A (en) | 2019-08-08 | 2019-08-08 | A kind of fire-retardant rapid-curing cutback glue and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110359281A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114714460A (en) * | 2022-04-15 | 2022-07-08 | 何菊 | Shaving board and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560039A (en) * | 2004-02-26 | 2005-01-05 | 湖南大学 | Tri(methyl)epoxy acrylate isocyanurate and synthesizing process thereof |
| CN101381445A (en) * | 2008-10-31 | 2009-03-11 | 北京理工大学 | Environment friendly non-halogen reacting fire-retardant aqueous polyurethane and preparation method thereof |
| CN106188562A (en) * | 2016-07-25 | 2016-12-07 | 太原理工大学 | A kind of ultrabranching polyamide carbon forming agent and preparation method thereof |
| CN106700081A (en) * | 2017-01-22 | 2017-05-24 | 太原理工大学 | Polysiloxane fire retardant containing nitrogen, phosphorus and silicon, and preparation method thereof |
| CN106700078A (en) * | 2017-01-22 | 2017-05-24 | 太原理工大学 | Hybridization structured polysiloxane flame retardant and preparation method thereof |
| CN106700920A (en) * | 2017-01-22 | 2017-05-24 | 太原理工大学 | Reaction type polysiloxane flame-retardant coating and preparation method thereof |
| CN107513356A (en) * | 2017-10-12 | 2017-12-26 | 柳州亚翔科技有限公司 | A kind of automotive trim formaldehyde-free glue and preparation method thereof |
| CN109929472A (en) * | 2017-12-15 | 2019-06-25 | 定陶宏瑞包装有限公司 | A kind of carton flame-retardant adhesive |
-
2019
- 2019-08-08 CN CN201910729398.5A patent/CN110359281A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560039A (en) * | 2004-02-26 | 2005-01-05 | 湖南大学 | Tri(methyl)epoxy acrylate isocyanurate and synthesizing process thereof |
| CN101381445A (en) * | 2008-10-31 | 2009-03-11 | 北京理工大学 | Environment friendly non-halogen reacting fire-retardant aqueous polyurethane and preparation method thereof |
| CN106188562A (en) * | 2016-07-25 | 2016-12-07 | 太原理工大学 | A kind of ultrabranching polyamide carbon forming agent and preparation method thereof |
| CN106700081A (en) * | 2017-01-22 | 2017-05-24 | 太原理工大学 | Polysiloxane fire retardant containing nitrogen, phosphorus and silicon, and preparation method thereof |
| CN106700078A (en) * | 2017-01-22 | 2017-05-24 | 太原理工大学 | Hybridization structured polysiloxane flame retardant and preparation method thereof |
| CN106700920A (en) * | 2017-01-22 | 2017-05-24 | 太原理工大学 | Reaction type polysiloxane flame-retardant coating and preparation method thereof |
| CN107513356A (en) * | 2017-10-12 | 2017-12-26 | 柳州亚翔科技有限公司 | A kind of automotive trim formaldehyde-free glue and preparation method thereof |
| CN109929472A (en) * | 2017-12-15 | 2019-06-25 | 定陶宏瑞包装有限公司 | A kind of carton flame-retardant adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 任庆利 等: ""镁铝水滑石阻燃料的研究"", 《绝缘材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114714460A (en) * | 2022-04-15 | 2022-07-08 | 何菊 | Shaving board and preparation method thereof |
| CN114714460B (en) * | 2022-04-15 | 2022-11-18 | 何菊 | Shaving board and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106700920B (en) | A kind of response type polysiloxanes flame retardant coating and preparation method thereof | |
| CN111072973B (en) | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant | |
| CN111849270B (en) | Nitrogen, phosphorus and silicon synergistic coal flame-retardant dust suppressant and preparation method thereof | |
| CA2817571C (en) | Formaldehyde free binder compositions with urea-aldehyde reaction products | |
| CN111378285B (en) | High-strength high-flame-retardant organic silicon foam material and preparation method thereof | |
| CN1900203A (en) | Water repellant curable aqueous compositions | |
| CN101792537A (en) | Silane coupling agent containing DOPO group and preparation method thereof | |
| CN106700081A (en) | Polysiloxane fire retardant containing nitrogen, phosphorus and silicon, and preparation method thereof | |
| CN111748249B (en) | Silicon-phosphorus synergistic coal flame-retardant dust suppressant and preparation method thereof | |
| CN111961075B (en) | Silicon-nitrogen flame-retardant precursor and preparation method thereof, silicon-nitrogen hybridized flame-retardant sol and preparation method thereof | |
| Cheng et al. | UV-curing behavior and properties of tri/di (acryloyloxyethyloxy) phenyl silane used for flame-retardant coatings | |
| CN110483577A (en) | A kind of P, N, Si ternary hybrid fire retardant and preparation method | |
| TW200904909A (en) | Modified expansible graphite by silane modifying agent and producing method thereof | |
| CN110359281A (en) | A kind of fire-retardant rapid-curing cutback glue and preparation method thereof | |
| CN109266007A (en) | Expandable flame retardant room temperature vulcanized silicone rubber formula and expandable flame retardant room temperature vulcanized silicone rubber | |
| CN102875816B (en) | Organosilicone modified halogen-free intumescent flame retardant and preparation method thereof | |
| CN1338539A (en) | Fiber coating material and coating liquid | |
| CN108384402A (en) | A kind of nano-zinc stannate fire retardant of nucleocapsid and its epoxy acrylate intumescent fire-retardant coating material for cooperateing with phosphorus nitrogen | |
| CN110511572A (en) | A kind of silicon hybridization composite flame-retardant agent of carbonaceous material and its preparation method and application | |
| CN110294846B (en) | Cage-net structure hybrid silsesquioxane flame retardant containing DOPO group and preparation method and application thereof | |
| CN111499838B (en) | DOPO-based triazole-containing curing agent and preparation method thereof, epoxy resin composition, cured product and application thereof | |
| JP2006526047A (en) | Method for producing polymeric material | |
| CN113402712B (en) | Phosphorus-containing ladder-shaped polysiloxane and preparation method and application thereof | |
| CN114148059A (en) | Shockproof sound-absorbing foam | |
| CN115322224B (en) | Preparation method of novel flame retardant, product thereof and application of novel flame retardant in cotton fibers |
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 | ||
| CB02 | Change of applicant information |
Address after: 241000 No.1 Houwang Road, Suncun Economic Development Zone, Fanchang County, Wuhu City, Anhui Province Applicant after: Anhui langlitong new material application Co.,Ltd. Address before: 241200 Fengdun Village, Sun Village, Fanchang County, Wuhu City, Anhui Province Applicant before: WUHU LITONG NEW MATERIAL Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191022 |
|
| RJ01 | Rejection of invention patent application after publication |