CN117535028A - Expansion type flame-retardant fireproof adhesive and preparation method thereof - Google Patents

Expansion type flame-retardant fireproof adhesive and preparation method thereof Download PDF

Info

Publication number
CN117535028A
CN117535028A CN202311350498.XA CN202311350498A CN117535028A CN 117535028 A CN117535028 A CN 117535028A CN 202311350498 A CN202311350498 A CN 202311350498A CN 117535028 A CN117535028 A CN 117535028A
Authority
CN
China
Prior art keywords
parts
modified
stirring
zinc borate
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
Application number
CN202311350498.XA
Other languages
Chinese (zh)
Inventor
潘林
詹才辉
杨泽生
郑锋
张焕园
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Sankeshu Coating Co ltd
Original Assignee
Sichuan Sankeshu Coating Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sichuan Sankeshu Coating Co ltd filed Critical Sichuan Sankeshu Coating Co ltd
Priority to CN202311350498.XA priority Critical patent/CN117535028A/en
Publication of CN117535028A publication Critical patent/CN117535028A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to an expansion type flame-retardant fireproof adhesive and a preparation method thereof, wherein the adhesive comprises the following components in parts by weight: 100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 15-20 parts of polydimethylsiloxane oil, 30-50 parts of nano calcium carbonate, 60-70 parts of modified hydromagnesite, 20-30 parts of modified zinc borate, 6-10 parts of nitrogenous organic flame retardant, 13-15 parts of crosslinking curing agent, 3-4 parts of silane coupling agent and 0.2-0.3 part of catalyst; the modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by hard butter and titanate coupling agent; the modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent. The invention takes alpha, omega-dihydroxyl polydimethylsiloxane as a main chain structure, is a non-carbon chain polymer, generates silicon dioxide after burning when meeting fire, does not generate toxic smoke such as carbon monoxide and the like, and is green and environment-friendly; meanwhile, the flame-retardant expansion, fire-isolating and smoke-suppressing effects of the flame-retardant adhesive are greatly improved through the compound use of the modified hydromagnesite, the modified zinc borate and the nitrogenous organic flame retardant.

Description

Expansion type flame-retardant fireproof adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of fireproof materials, in particular to an expansion type flame-retardant fireproof adhesive and a preparation method thereof.
Background
In order to reduce fire hazard, the living building issues national standard GB 55037-2022 general Specification for building fire prevention, aims to prevent building fire, reduce fire hazard, and ensure personal and property safety, and provides fire protection requirements for various buildings except civil explosive building from links of planning, design, construction, use, maintenance and the like. The use of fire-resistant materials therefore becomes of importance.
The fireproof sealant is a common fireproof blocking material and is mainly used for fireproof separation formed when various cables, ship bodies, doors and windows, electrical equipment, conveying pipes and the like pass through walls and floors. The existing fireproof sealant material generally has the problems of poor flame retardance, expansibility, adhesiveness and the like, so that the fireproof flame-retardant sealing effect is unsatisfactory. For example, chinese patent CN103773254a discloses a fireproof glue containing modified talcum powder, which uses carbon-based compounds such as styrene, bromocarbon phenolic resin and the like as main components, and the prepared product has good acid and alkali resistance and high temperature resistance, but poor flame retardant and fireproof performance and expansion performance; chinese patent CN112358818A discloses a fire-proof glue, which is composed of liquid sodium silicate, silica sol, polyvinyl alcohol, defoamer, heat absorbing powder, expansion powder, etc., but the fire-proof glue is mainly applied to metal foil fire prevention, and has poor adhesion with building materials and limited application; chinese patent CN1438289A discloses a neutral silicone fireproof sealant and a manufacturing method thereof, which have certain flame retardant property, but have no expansion property when meeting fire, have poor plugging effect and can not effectively prevent fire from spreading.
In view of this, the present invention has been made.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention provides an expansion type flame-retardant fireproof adhesive and a preparation method thereof, wherein the expansion type flame-retardant fireproof adhesive is not easy to burn when meeting fire, can rapidly expand and seal gaps, and effectively plays roles of preventing fires, retarding flame, sealing fire and isolating smoke; meanwhile, the problems of low bonding strength, poor processing performance, poor environmental protection performance and the like of some fireproof adhesives are solved.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides an expansion type flame-retardant fireproof adhesive, which comprises the following components in parts by weight:
100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 15-20 parts of polydimethylsiloxane oil, 30-50 parts of nano calcium carbonate, 60-70 parts of modified hydromagnesite, 20-30 parts of modified zinc borate, 6-10 parts of nitrogenous organic flame retardant, 13-15 parts of crosslinking curing agent, 3-4 parts of silane coupling agent and 0.2-0.3 part of catalyst;
the modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by hard butter and titanate coupling agent;
the modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent.
The expansion type flame-retardant fireproof adhesive provided by the invention takes alpha, omega-dihydroxy polydimethylsiloxane as a main chain structure, is a non-carbon chain polymer, generates silicon dioxide after being burnt by fire, does not generate toxic smoke such as carbon monoxide and the like, and is environment-friendly; meanwhile, the flame-retardant expansion, fire-isolating and smoke-suppressing effects of the flame-retardant adhesive are greatly improved through the compound use of the modified hydromagnesite, the modified zinc borate and the nitrogenous organic flame retardant. Compared with common fireproof glue in the market, when the fire is received, the modified hydromagnesite and the modified zinc borate in the fireproof glue are firstly thermally decomposed to release crystal water, so that the effects of absorbing heat, cooling and diluting combustible gas are achieved, and meanwhile, magnesium oxide and diboron trioxide are generated to be foamed and expanded to form a uniform and compact heat-insulating oxide layer, so that the generation of the combustible gas can be restrained, and the oxidation reaction and the thermal decomposition can be slowed down or prevented; and the compounded nitrogen-containing organic flame retardant is heated and decomposed to generate a large amount of nitrogen, so that flame can be extinguished, the expansion multiple of an oxide layer can be increased, the expansion performance is more than 300%, and the fire-resistant time is prolonged. In addition, the invention adopts the water magnesite and zinc borate which are subjected to surface modification treatment, so that on one hand, the oil absorption value can be reduced, and the construction performance can be improved; on the other hand, the dispersion stability and compatibility with the polymer can be enhanced, the problem that the mechanical property of the material is reduced due to the high addition amount of the inorganic flame retardant component is solved, the fireproof flame retardance and the physicochemical property of the fireproof adhesive are further improved, and the fireproof adhesive is free from cracking after long-term use.
Optionally, the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 5000-200000 mPa.s at 25 ℃; the viscosity of the polydimethyl silicone oil at 25 ℃ is 50-1000 mPas.
Optionally, the nano calcium carbonate is subjected to surface modification treatment by a silane coupling agent or stearic acid, the water content is less than or equal to 0.3%, the average particle size is 40-100 nm, and the specific surface area is 20-30 m 2 /g。
According to the description, the oil absorption value of the material is low, the compatibility with the polymer is good, and the construction performance and mechanical property of the product can be improved.
Optionally, the preparation method of the modified hydromagnesite comprises the following steps: 100 parts of superfine water magnesite powder with the average particle diameter D50 of 1.5-2 mu m is added into a high-speed mixer and heated to 90-95 ℃, then 0.8-1.2 parts of stearic acid and 0.8-1.2 parts of titanate coupling agent are added, the high-speed disperser is started, stirring and modification are carried out for 30-35 min at the speed of 700-800 r/min, and the mixture is uniformly mixed, thus obtaining the product.
According to the above description, the surface of the hydromagnesite powder has a hydrophilic and oleophobic polar state, has poor compatibility with a polymer matrix, and the hydromagnesite powder can be endowed with a low oil absorption value by modifying the hydromagnesite powder together with a titanate coupling agent, so that the compatibility with the matrix is improved, and the mechanical property of the product is not deteriorated even if the hydromagnesite powder is filled in a high proportion. When the modified water magnesite burns when meeting fire, the modified water magnesite can absorb heat to decompose and release crystal water to dilute the oxygen concentration, and magnesium oxide coating is formed on the surface of the material to play a role in isolating oxygen and heat, so that flame spread is prevented.
Optionally, the preparation method of the modified zinc borate comprises the following steps: adding 100 parts of superfine zinc borate powder with the average particle diameter D50 of 2-3 mu m into a high-speed mixer, heating to 95-100 ℃, then adding 0.8-1 part of gamma-glycidoxypropyl trimethoxysilane and 1-1.2 parts of stearic acid, starting the high-speed disperser, stirring and modifying at the speed of 800-900 r/min for 25-30 min, and uniformly mixing to obtain the zinc borate powder.
From the above description, it is known that zinc borate is a hydrophilic and oleophobic polar inorganic compound, and is difficult to uniformly disperse when blended with a polymer. The silane coupling agent and stearic acid are compounded to carry out surface modification, so that the oil absorption value of the polymer can be reduced, the aggregation of the polymer in the polymer can be reduced, the consumption of the polymer can be increased, the flame retardant effect can be further improved, and the mechanical property is not lost. The introduction of the modified zinc borate is heated and decomposed to generate crystal water and a boron oxide expansion layer when the material burns, and the crystal water and an oxidation protection layer are continuously generated at different temperatures under the synergistic effect with the modified water magnesite.
Optionally, the nitrogen-containing organic flame retardant is at least one of 5-aminotetrazole, 5-acetamido tetrazole, 1-methyl-5-aminotetrazole, and 2-phenyl-5-aminotetrazole.
From the above description, it is known that nitrogen-containing organic flame retardants decompose large amounts of nitrogen at high temperatures, causing the oxide layer to expand rapidly, blocking gaps, and impeding flame and volatiles from escaping.
Optionally, the crosslinking curing agent is formed by mixing vinyl tributyl ketoxime silane and methyl tributyl ketoxime silane according to a mass ratio of 1:6-8; the silane coupling agent is formed by mixing gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and gamma- (2, 3-glycidoxy) propyl trimethoxysilane according to a mass ratio of 1:0.5-1:1-3; the catalyst is at least one of dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin diacetate and stannous octoate.
According to the description, the cross-linking curing agent mixed by a specific proportion can endow the fireproof adhesive with better elasticity and is not easy to crack; the specific three silane coupling agents are compounded for use, so that the bonding performance of the product can be synergistically improved, and the prepared product has a good bonding effect on common building materials; the adoption of the organotin catalyst can better control the curing speed of the fireproof glue.
The invention also provides a preparation method of the expansion type flame-retardant fireproof adhesive, which comprises the following steps:
s1, preparing modified hydromagnesite and modified zinc borate;
s2, adding alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, modified hydromagnesite, modified zinc borate and nitrogen-containing organic flame retardant into a high-speed dispersing machine according to the proportion, stirring and dewatering, uniformly mixing to prepare a base material, and cooling to room temperature;
s3, adding the crosslinking curing agent into the base material according to the proportion, stirring for the first time, and then adding the silane coupling agent and the catalyst for the second time to obtain the modified polyurethane adhesive.
The preparation process of the intumescent flame retardant fireproof adhesive is simple, safe and environment-friendly in the production process, free of addition of organic solvents and release of toxic gases, convenient to use and single-component curing; meanwhile, compared with the flame retardant glue prepared by the traditional halogen flame retardant, the flame retardant glue has no toxic and harmful gas release in the combustion process, and is environment-friendly.
Optionally, the stirring and dewatering conditions in the step S2 are as follows: the temperature is 110-120 ℃, the vacuum degree is-0.095 to-0.08 Mpa, the stirring speed is 600-800 r/min, and the stirring water removal time is 120-150 min.
Optionally, the primary stirring condition in step S3 is: the temperature is 25-40 ℃, the vacuum degree is-0.09 to-0.08 Mpa, the stirring speed is 100-200 r/min, and the stirring time is 10-20 min; the secondary stirring conditions are as follows: the temperature is 25-40 ℃, the vacuum degree is-0.095 to-0.08 Mpa, the stirring speed is 400-600 r/min, and the stirring time is 20-30 min.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides an expansion type flame-retardant fireproof adhesive, which comprises the following components in parts by weight:
100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 15-20 parts of polydimethylsiloxane oil, 30-50 parts of nano calcium carbonate, 60-70 parts of modified hydromagnesite, 20-30 parts of modified zinc borate, 6-10 parts of nitrogenous organic flame retardant, 13-15 parts of crosslinking curing agent, 3-4 parts of silane coupling agent and 0.2-0.3 part of catalyst;
the modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by hard butter and titanate coupling agent;
the modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent.
The viscosity of the alpha, omega-dihydroxy polydimethylsiloxane at 25 ℃ is 5000-200000 mPa.s; the viscosity of the polydimethyl silicone oil at 25 ℃ is 50-1000 mPas.
Preferably, the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 20000-80000 mPa.s at 25 ℃; the viscosity of the polydimethyl silicone oil at 25 ℃ is 100-500 mPas.
The nano calcium carbonate is subjected to surface modification treatment by a silane coupling agent or stearic acid, the water content is less than or equal to 0.3%, the average particle size is 40-100 nm, and the specific surface area is 20-30 m 2 /g。
The preparation method of the modified hydromagnesite comprises the following steps: 100 parts of superfine water magnesite powder with the average particle diameter D50 of 1.5-2 mu m is added into a high-speed mixer and heated to 90-95 ℃, then 0.8-1.2 parts of stearic acid and 0.8-1.2 parts of titanate coupling agent are added, the high-speed disperser is started, stirring and modification are carried out for 30-35 min at the speed of 700-800 r/min, and the mixture is uniformly mixed, thus obtaining the product.
Preferably, the stearic acid is a product provided by Nanjing chemical company, inc.; the titanate coupling agent adopts JN-201 titanate coupling agent of Dinghai plastic chemical engineering Co.
The preparation method of the modified zinc borate comprises the following steps: adding 100 parts of superfine zinc borate powder with the average particle diameter D50 of 2-3 mu m into a high-speed mixer, heating to 95-100 ℃, then adding 0.8-1 part of gamma-glycidoxypropyl trimethoxysilane and 1-1.2 parts of stearic acid, starting the high-speed disperser, stirring and modifying at the speed of 800-900 r/min for 25-30 min, and uniformly mixing to obtain the zinc borate powder.
The nitrogen-containing organic flame retardant is at least one of 5-aminotetrazole, 5-acetamido tetrazole, 1-methyl-5-aminotetrazole and 2-phenyl-5-aminotetrazole.
Preferably, the nitrogen-containing organic flame retardant employs 5-aminotetrazole or 5-acetamido tetrazole having an average particle diameter D50 of 10-15 μm.
The cross-linking curing agent is formed by mixing vinyl tributyl ketoxime silane and methyl tributyl ketoxime silane according to a mass ratio of 1:6-8; the silane coupling agent is formed by mixing gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and gamma- (2, 3-glycidoxy) propyl trimethoxysilane according to a mass ratio of 1:0.5-1:1-3; the catalyst is at least one of dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin diacetate and stannous octoate.
It is prepared by the following method:
s1, preparing modified hydromagnesite and modified zinc borate.
S2, adding alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, modified hydromagnesite, modified zinc borate and nitrogen-containing organic flame retardant into a high-speed dispersing machine according to the proportion, stirring and dewatering, uniformly mixing to prepare a base material, and cooling to room temperature;
the stirring and dewatering conditions are as follows: the temperature is 110-120 ℃, the vacuum degree is-0.095 to-0.08 Mpa, the stirring speed is 600-800 r/min, and the stirring water removal time is 120-150 min.
S3, adding the crosslinking curing agent into the base material according to the proportion, stirring for the first time, and then adding the silane coupling agent and the catalyst for the second time to obtain the modified polyurethane adhesive;
the primary stirring conditions are as follows: the temperature is 25-40 ℃, the vacuum degree is-0.09 to-0.08 Mpa, the stirring speed is 100-200 r/min, and the stirring time is 10-20 min;
the secondary stirring conditions are as follows: the temperature is 25-40 ℃, the vacuum degree is-0.095 to-0.08 Mpa, the stirring speed is 400-600 r/min, and the stirring time is 20-30 min.
Example 1
An expansion type flame-retardant fireproof adhesive comprises the following components in parts by weight:
100 parts of alpha, omega-dihydroxypolydimethylsiloxane (viscosity: 50000 mPa.s), 15 parts of polydimethylsiloxane oil (viscosity: 100 mPa.s), 30 parts of nano calcium carbonate, 65 parts of modified hydromagnesite, 30 parts of modified zinc borate, 8 parts of nitrogenous organic flame retardant (5-aminotetrazole), 13 parts of crosslinking curing agent (vinyl tributyl ketoxime silane: methyltributylketone oxime silane=1:8), 3.5 parts of silane coupling agent (gamma-aminopropyl triethoxysilane: N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane: gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane=1:0.6:2) and 0.25 parts of catalyst (dibutyl tin dilaurate).
The modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by a hard acid ester and a titanate coupling agent, and the specific preparation method comprises the following steps: 100 parts of superfine water magnesite powder with the average particle diameter D50 of 1.5-2 mu m is added into a high-speed mixer and heated to 95 ℃, then 0.8 part of stearic acid and 1.2 parts of titanate coupling agent are added, the high-speed disperser is started, stirring and modification are carried out for 35min at the speed of 800r/min, and the mixture is uniformly mixed, thus obtaining the product.
The modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent, and the specific preparation method comprises the following steps: adding 100 parts of superfine zinc borate powder with the average particle diameter D50 of 2-3 mu m into a high-speed mixer, heating to 100 ℃, then adding 1 part of gamma-glycidoxypropyl trimethoxy silane and 1.2 parts of stearic acid, starting the high-speed disperser, stirring and modifying for 30min at the speed of 800r/min, and uniformly mixing to obtain the zinc borate powder.
It is prepared by the following method:
s1, preparing modified hydromagnesite and modified zinc borate.
S2, adding alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, modified hydromagnesite, modified zinc borate and nitrogenous organic flame retardant into a high-speed dispersing machine according to the proportion, heating to 110 ℃, adjusting the stirring speed to 800r/min, stirring and dewatering for 120min under the vacuum degree of-0.095 Mpa, uniformly mixing to prepare a base material, and cooling to room temperature.
S3, adding the crosslinking curing agent into the base material according to the proportion, controlling the temperature to be 35 ℃, stirring at the speed of 200r/min, stirring for 20min under the vacuum degree of-0.09 Mpa, adding the silane coupling agent and the catalyst, controlling the temperature to be 40 ℃, stirring at the speed of 500r/min, and stirring for 25min under the vacuum degree of-0.08 Mpa.
Example 2
An expansion type flame-retardant fireproof adhesive comprises the following components in parts by weight:
100 parts of alpha, omega-dihydroxypolydimethylsiloxane (with the viscosity of 20000 mPa.s), 20 parts of polydimethylsiloxane oil (with the viscosity of 100 mPa.s), 50 parts of nano calcium carbonate, 70 parts of modified hydromagnesite, 20 parts of modified zinc borate, 10 parts of nitrogenous organic flame retardant (5-acetamido tetrazole), 14 parts of cross-linking curing agent (vinyl tributyl ketoximino silane: methyltributylketono-oxime silane=1:7), 3 parts of silane coupling agent (gamma-aminopropyl triethoxy silane: N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane: gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane=1:0.5:1) and 0.3 parts of catalyst (dibutyl tin dioctanoate).
The modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by a hard acid ester and a titanate coupling agent, and the specific preparation method comprises the following steps: 100 parts of superfine water magnesite powder with the average particle diameter D50 of 1.5-2 mu m is added into a high-speed mixer and heated to 90 ℃, then 1.2 parts of stearic acid and 1.2 parts of titanate coupling agent are added, the high-speed disperser is started, stirring and modification are carried out for 35min at the speed of 700r/min, and the mixture is uniformly mixed, thus obtaining the product.
The modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent, and the specific preparation method comprises the following steps: 100 parts of superfine zinc borate powder with the average particle diameter D50 of 2-3 mu m is added into a high-speed mixer and heated to 100 ℃, then 1 part of gamma-glycidoxypropyl trimethoxy silane and 1.2 parts of stearic acid are added, the high-speed disperser is started, stirring and modification are carried out for 25min at the speed of 900r/min, and the mixture is uniformly mixed, thus obtaining the zinc borate powder.
It is prepared by the following method:
s1, preparing modified hydromagnesite and modified zinc borate.
S2, adding alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, modified hydromagnesite, modified zinc borate and nitrogenous organic flame retardant into a high-speed dispersing machine according to the proportion, heating to 120 ℃, adjusting the stirring speed to 600r/min, stirring and dewatering for 150min under the vacuum degree of-0.095 Mpa, uniformly mixing to prepare a base material, and cooling to room temperature.
S3, adding the crosslinking curing agent into the base material according to the proportion, controlling the temperature to be 30 ℃, stirring at the speed of 100r/min, stirring for 20min under the vacuum degree of-0.08 Mpa, adding the silane coupling agent and the catalyst, controlling the temperature to be 35 ℃, stirring at the speed of 500r/min, and stirring for 25min under the vacuum degree of-0.095 Mpa.
Example 3
An expansion type flame-retardant fireproof adhesive comprises the following components in parts by weight:
100 parts of alpha, omega-dihydroxypolydimethylsiloxane (viscosity is 80000 mPa.s), 18 parts of polydimethylsiloxane oil (viscosity is 500 mPa.s), 35 parts of nano calcium carbonate, 60 parts of modified hydromagnesite, 25 parts of modified zinc borate, 6 parts of nitrogenous organic flame retardant (1-methyl-5-aminotetrazole), 15 parts of cross-linking curing agent (vinyltributyl ketoxime silane: methyltributyloxy silane=1:8), 3.5 parts of silane coupling agent (gamma-aminopropyl triethoxysilane: N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane: gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane=1:1:3) and 0.3 part of catalyst (stannous octoate).
The modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by a hard acid ester and a titanate coupling agent, and the specific preparation method comprises the following steps: 100 parts of superfine water magnesite powder with the average particle diameter D50 of 1.5-2 mu m is added into a high-speed mixer and heated to 93 ℃, then 1 part of stearic acid and 1.2 parts of titanate coupling agent are added, the high-speed disperser is started, stirring and modification are carried out for 35min at the speed of 750r/min, and the mixture is uniformly mixed, thus obtaining the product.
The modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent, and the specific preparation method comprises the following steps: 100 parts of superfine zinc borate powder with the average particle diameter D50 of 2-3 mu m is added into a high-speed mixer and heated to 98 ℃, then 0.9 part of gamma-glycidoxypropyl trimethoxysilane and 1.1 part of stearic acid are added, the high-speed disperser is started, stirring and modification are carried out for 30min at the speed of 820r/min, and the mixture is uniformly mixed, thus obtaining the zinc borate powder.
It is prepared by the following method:
s1, preparing modified hydromagnesite and modified zinc borate.
S2, adding alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, modified hydromagnesite, modified zinc borate and nitrogenous organic flame retardant into a high-speed dispersing machine according to the proportion, heating to 120 ℃, adjusting the stirring speed to 650r/min, stirring and dehydrating for 130min under the vacuum degree of-0.085 Mpa, uniformly mixing to prepare a base material, and cooling to room temperature.
S3, adding the crosslinking curing agent into the base material according to the proportion, controlling the temperature to be 40 ℃, stirring at the stirring speed of 160r/min, stirring for 15min under the vacuum degree of-0.08 Mpa, adding the silane coupling agent and the catalyst, controlling the temperature to be 28 ℃, stirring at the stirring speed of 600r/min, and stirring for 30min under the vacuum degree of-0.08 Mpa.
Example 4
An expansion type flame-retardant fireproof adhesive comprises the following components in parts by weight:
100 parts of alpha, omega-dihydroxypolydimethylsiloxane (viscosity is 80000 mPa.s), 20 parts of polydimethylsiloxane oil (viscosity is 500 mPa.s), 40 parts of nano calcium carbonate, 60 parts of modified hydromagnesite, 25 parts of modified zinc borate, 6 parts of nitrogenous organic flame retardant (5-aminotetrazole), 13 parts of crosslinking curing agent (vinyl tributyl ketoxime silane: methyltributylketone oxime silane=1:6), 4 parts of silane coupling agent (gamma-aminopropyl triethoxysilane: N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane: gamma- (2, 3-glycidoxy) propyl trimethoxysilane=1:0.8:2.5) and 0.2 parts of catalyst (stannous octoate).
The modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by a hard acid ester and a titanate coupling agent, and the specific preparation method comprises the following steps: 100 parts of superfine water magnesite powder with the average particle diameter D50 of 1.5-2 mu m is added into a high-speed mixer and heated to 93 ℃, then 1 part of stearic acid and 1.2 parts of titanate coupling agent are added, the high-speed disperser is started, stirring and modification are carried out for 35min at the speed of 750r/min, and the mixture is uniformly mixed, thus obtaining the product.
The modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent, and the specific preparation method comprises the following steps: 100 parts of superfine zinc borate powder with the average particle diameter D50 of 2-3 mu m is added into a high-speed mixer and heated to 98 ℃, then 1 part of gamma-glycidoxypropyl trimethoxy silane and 1.1 part of stearic acid are added, the high-speed disperser is started, stirring and modification are carried out for 30min at the speed of 820r/min, and the mixture is uniformly mixed, thus obtaining the zinc borate powder.
It is prepared by the following method:
s1, preparing modified hydromagnesite and modified zinc borate.
S2, adding alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, modified hydromagnesite, modified zinc borate and nitrogenous organic flame retardant into a high-speed dispersing machine according to the proportion, heating to 120 ℃, adjusting the stirring speed to 650r/min, stirring and dehydrating for 130min under the vacuum degree of-0.085 Mpa, uniformly mixing to prepare a base material, and cooling to room temperature.
S3, adding the crosslinking curing agent into the base material according to the proportion, controlling the temperature to be 30 ℃, stirring at the stirring speed of 160r/min, stirring for 15min under the vacuum degree of-0.08 Mpa, adding the silane coupling agent and the catalyst, controlling the temperature to be 28 ℃, stirring at the stirring speed of 600r/min, and stirring for 30min under the vacuum degree of-0.08 Mpa.
Comparative example 1
The main difference between this comparative example and example 3 is that the modified water magnesite was replaced with ordinary water magnesite Dan Dengliang, the modified zinc borate was replaced with an equal amount of ordinary zinc borate, and no nitrogen-containing organic flame retardant was added.
Comparative example 2
100 parts of alpha, omega-dihydroxypolydimethylsiloxane with the viscosity of 20000 mPas, 18 parts of polydimethylsiloxane with the viscosity of 100 mPas and 120 parts of nano calcium carbonate are added into a high-speed dispersing machine, the temperature is raised to 120 ℃, the stirring speed is adjusted to 650r/min, the water is removed for 130min under the vacuum degree of minus 0.085mPa, the mixture is uniformly mixed to prepare a base material, and the base material is cooled to the room temperature.
And adding 15 parts of a crosslinking curing agent (methyl tributyl ketoxime silane) into the base material, controlling the temperature to be 40 ℃, stirring at the stirring speed of 160r/min, stirring for 15min under the vacuum degree of-0.08 Mpa, adding 3.5 parts of a silane coupling agent (gamma-aminopropyl triethoxysilane: gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane=1:1) and 0.25 part of a catalyst (stannous octoate), controlling the temperature to be 28 ℃, stirring at the stirring speed of 600r/min, and stirring for 30min under the vacuum degree of-0.08 Mpa.
Comparative example 3
100 parts of alpha, omega-dihydroxypolydimethylsiloxane with the viscosity of 80000 mPas, 20 parts of polydimethylsiloxane with the viscosity of 500 mPas, 50 parts of nano calcium carbonate, 60 parts of modified hydromagnesite, 25 parts of modified zinc borate and 6 parts of melamine are added into a high-speed dispersing machine, the temperature is raised to 120 ℃, the stirring speed is regulated to 650r/min, the dehydration is carried out for 130min under the vacuum degree of-0.085 MPa, the mixture is uniformly mixed to prepare a base material, and the base material is cooled to room temperature.
13 parts of cross-linking curing agent (vinyl tributyl ketoxime silane: methyl tributyl ketoxime silane=1:6) are added into the base material, the temperature is controlled to be 30 ℃, the stirring speed is 160r/min, the mixture is stirred for 15min under the vacuum degree of-0.08 Mpa, 4 parts of silane coupling agent (gamma-aminopropyl triethoxysilane: N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane: gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane=1:0.8:2.5) and 0.2 part of catalyst (stannous octoate) are added, the temperature is controlled to be 28 ℃, the stirring speed is 600r/min, and the mixture is stirred for 30min under the vacuum degree of-0.08 Mpa.
Comparative example 4
The comparative example is different from example 4 in that 60 parts of modified hydromagnesite and 25 parts of modified zinc borate are replaced by a flame retardant system consisting of 45 parts of modified aluminum hydroxide, 20 parts of modified magnesium hydroxide and 20 parts of modified magnesium carbonate (the above substances are modified with stearic acid).
The flame-retardant and flame-retardant adhesives prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to performance test according to the test methods of standard GB 23864-2009 fire-retardant plugging materials and GB/T13477 building sealing materials, and the results are recorded in Table 1.
TABLE 1 Performance test results
As can be seen from Table 1, the intumescent flame retardant and fire retardant glue prepared by the embodiment of the invention has excellent flame retardant property, intumescent property, physicochemical property and environmental protection property, can meet the performance requirements in the field, the sealing device is particularly suitable for sealing and installing various building needing fireproof bonding sealing and plugging places such as various fireproof doors and windows, fireproof partition walls, fireproof roller shutters, fireproof curtain walls, pipeline perforation of fireproof partition walls and gaps between curtain walls, indoor decoration fireproof and outer wall heat preservation fireproof.
As can be seen from comparative example 1, the fireproof glue prepared by the method has fire resistance and flame retardance meeting the standards, but has high oil absorption value and poor compatibility with polymers due to the adoption of unmodified superfine hydromagnesite and superfine zinc borate powder, so that the extrusion performance and stretching adhesiveness of the product are poor, and the service performance of the product is affected; meanwhile, although the ordinary water magnesite and the ordinary zinc borate have certain expansibility, the expansion performance of the product is poor because the ordinary water magnesite and the ordinary zinc borate are not matched with the nitrogen-containing organic flame retardant for use, and the standard of 300% cannot be met. The test result of comparative example 2 shows that the silicone fireproof adhesive prepared by replacing flame retardant filler modified hydromagnesite and modified zinc borate with nano calcium carbonate has better extrudability and stretching adhesion performance, but the fire resistance and flame resistance can not meet the standard requirements, and has no expansion performance. The comparative example 3 adopts the traditional nitrogen-containing compound melamine as a nitrogen source for preparing the fireproof glue, the basic index of the product meets the requirement, but the expansion performance is obviously inferior to that of the aminotetrazole nitrogen-containing flame retardant adopted in the embodiment of the invention, which also shows that the aminotetrazole is adopted as the nitrogen source for generating stable and large amount of nitrogen, and the nitrogen is compounded with the modified hydromagnesite and the modified zinc borate, so that the expansion rate of the flame-retardant fireproof glue prepared by taking polydimethylsiloxane as a base material can be greatly improved; meanwhile, melamine is heated to decompose and release highly toxic cyanide gas, which does not meet the environmental protection and safety requirements. Compared with the example 4, the comparative example 4 uses the modified aluminum hydroxide, the modified magnesium hydroxide and the modified magnesium carbonate as the flame retardant filler and the aminotetrazole nitrogen-containing compound in a compounding way, the flame retardance and the fire resistance of the product meet the requirements, but the extrusion property and the tensile bonding strength are reduced to some extent, and the expansibility does not reach the standard.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. An expansion type flame-retardant fireproof adhesive comprises the following components in parts by weight:
100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 15-20 parts of polydimethylsiloxane oil, 30-50 parts of nano calcium carbonate, 60-70 parts of modified hydromagnesite, 20-30 parts of modified zinc borate, 6-10 parts of nitrogenous organic flame retardant, 13-15 parts of crosslinking curing agent, 3-4 parts of silane coupling agent and 0.2-0.3 part of catalyst;
the modified hydromagnesite is superfine hydromagnesite subjected to surface modification treatment by hard butter and titanate coupling agent;
the modified zinc borate is superfine zinc borate subjected to surface modification treatment by stearic acid and a silane coupling agent.
2. The intumescent flame retardant and fire retardant gum of claim 1, wherein the α, ω -dihydroxy polydimethylsiloxane has a viscosity of 5000-200000 mPa-s at 25 ℃; the viscosity of the polydimethyl silicone oil at 25 ℃ is 50-1000 mPas.
3. The intumescent flame retardant and fire retardant glue of claim 1 wherein saidThe nano calcium carbonate is subjected to surface modification treatment by a silane coupling agent or stearic acid, the water content is less than or equal to 0.3%, the average particle size is 40-100 nm, and the specific surface area is 20-30 m 2 /g。
4. The intumescent flame retardant and fire resistant glue of claim 1, wherein the preparation method of the modified hydromagnesite comprises the following steps: 100 parts of superfine water magnesite powder with the average particle diameter D50 of 1.5-2 mu m is added into a high-speed mixer and heated to 90-95 ℃, then 0.8-1.2 parts of stearic acid and 0.8-1.2 parts of titanate coupling agent are added, the high-speed disperser is started, stirring and modification are carried out for 30-35 min at the speed of 700-800 r/min, and the mixture is uniformly mixed, thus obtaining the product.
5. The intumescent flame retardant and fire resistant glue of claim 1, wherein the preparation method of the modified zinc borate is as follows: adding 100 parts of superfine zinc borate powder with the average particle diameter D50 of 2-3 mu m into a high-speed mixer, heating to 95-100 ℃, then adding 0.8-1 part of gamma-glycidoxypropyl trimethoxysilane and 1-1.2 parts of stearic acid, starting the high-speed disperser, stirring and modifying at the speed of 800-900 r/min for 25-30 min, and uniformly mixing to obtain the zinc borate powder.
6. The intumescent flame retardant and fire retardant gum of claim 1, wherein the nitrogen-containing organic flame retardant is at least one of 5-aminotetrazole, 5-acetamido tetrazole, 1-methyl-5-aminotetrazole, and 2-phenyl-5-aminotetrazole.
7. The intumescent flame-retardant and fire-retardant glue of claim 1, wherein the cross-linking curing agent is formed by mixing vinyl tributyl ketoxime silane and methyl tributyl ketoxime silane according to a mass ratio of 1:6-8; the silane coupling agent is formed by mixing gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and gamma- (2, 3-glycidoxy) propyl trimethoxysilane according to a mass ratio of 1:0.5-1:1-3; the catalyst is at least one of dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin diacetate and stannous octoate.
8. The preparation method of the expansion type flame-retardant fireproof adhesive comprises the following steps:
s1, preparing modified hydromagnesite and modified zinc borate;
s2, adding alpha, omega-dihydroxyl polydimethylsiloxane, nano calcium carbonate, modified hydromagnesite, modified zinc borate and nitrogen-containing organic flame retardant into a high-speed dispersing machine according to the proportion, stirring and dewatering, uniformly mixing to prepare a base material, and cooling to room temperature;
s3, adding the crosslinking curing agent into the base material according to the proportion, stirring for the first time, and then adding the silane coupling agent and the catalyst for the second time to obtain the modified polyurethane adhesive.
9. The method for preparing the intumescent flame retardant and fire resistant adhesive of claim 8, wherein the stirring and dewatering conditions in the step S2 are as follows: the temperature is 110-120 ℃, the vacuum degree is-0.095 to-0.08 Mpa, the stirring speed is 600-800 r/min, and the stirring water removal time is 120-150 min.
10. The method for preparing the intumescent flame retardant and fire resistant adhesive of claim 8, wherein the primary stirring condition in step S3 is: the temperature is 25-40 ℃, the vacuum degree is-0.09 to-0.08 Mpa, the stirring speed is 100-200 r/min, and the stirring time is 10-20 min; the secondary stirring conditions are as follows: the temperature is 25-40 ℃, the vacuum degree is-0.095 to-0.08 Mpa, the stirring speed is 400-600 r/min, and the stirring time is 20-30 min.
CN202311350498.XA 2023-10-18 2023-10-18 Expansion type flame-retardant fireproof adhesive and preparation method thereof Pending CN117535028A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311350498.XA CN117535028A (en) 2023-10-18 2023-10-18 Expansion type flame-retardant fireproof adhesive and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311350498.XA CN117535028A (en) 2023-10-18 2023-10-18 Expansion type flame-retardant fireproof adhesive and preparation method thereof

Publications (1)

Publication Number Publication Date
CN117535028A true CN117535028A (en) 2024-02-09

Family

ID=89792733

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311350498.XA Pending CN117535028A (en) 2023-10-18 2023-10-18 Expansion type flame-retardant fireproof adhesive and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117535028A (en)

Similar Documents

Publication Publication Date Title
CN106833478B (en) High-performance flame-retardant two-component silane modified polyether sealant and preparation method thereof
CN110982185A (en) Fireproof sealing rubber material
CN102634351B (en) Aqueous halogen-free flexible fireproof plugging material
CN101747859A (en) Silicone fireproof sealant for construction and preparation method thereof
CN109401634B (en) Flame-retardant smoke-inhibiting ceramizable room temperature vulcanized organosilicon sealant and preparation method thereof
CN103160239A (en) High-displacement-ability silicone fire-proof sealing glue and manufacturing method of the same
CN101629063A (en) Expanding type flame-resistant silicone sealant and preparation method thereof
CN101397488A (en) Fireproof elastic sealant and preparation method thereof
CN113122124B (en) Expansion type flame-retardant heat-insulating fireproof coating and preparation method thereof
CN111500071A (en) Single-component flame-retardant silica gel foam material and preparation method thereof
CN110066638A (en) A kind of fire prevention silicone sealant of high temperature resistant ablation and preparation method thereof
CN104692758A (en) Smoke-suppressing type outdoor flame retardant steel structure fireproof coating
CN111154302A (en) Water-based inorganic intumescent fire-retardant coating and preparation method thereof
CN112745678B (en) Sealing rubber strip for building and preparation method thereof
CN112961500A (en) Non-solidified type sealing fireproof moistureproof silica gel mud and preparation method thereof
CN113185875A (en) Fireproof coating and preparation method thereof
CN117535028A (en) Expansion type flame-retardant fireproof adhesive and preparation method thereof
CN109401406B (en) Intumescent smoke-suppressing fire retardant for water-based paint and preparation method thereof
CN105315956A (en) Novel rapidly fireproof sealant for building
KR20160087610A (en) Aqueous Inorganic Incombustible expanded Adhesive Composition and Preparation Method Thereof
CN114621506B (en) Non-solidification type flexible organic putty and preparation method thereof
CN110003844B (en) Preparation method of ceramic fireproof silicone sealant
CN112778765A (en) Composite flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof
CN112724676A (en) Ceramic room temperature curing silicone rubber and preparation method thereof
CN112048152A (en) Flame-retardant sealing material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication