CN115594792A - Phosphorus-sulfur synergistic flame-retardant composition, and preparation method and application thereof - Google Patents

Phosphorus-sulfur synergistic flame-retardant composition, and preparation method and application thereof Download PDF

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CN115594792A
CN115594792A CN202211377923.XA CN202211377923A CN115594792A CN 115594792 A CN115594792 A CN 115594792A CN 202211377923 A CN202211377923 A CN 202211377923A CN 115594792 A CN115594792 A CN 115594792A
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phosphorus
sulfur
retardant
flame
monomer
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宋平安
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Ningbo Puduo Yike Technology Development Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D141/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

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Abstract

The invention discloses a phosphorus-sulfur synergistic flame-retardant composition, a preparation method and application thereof, and relates to the field of preparation of flame-retardant chemical materials, wherein the composition comprises the following components in parts by mole: 30-55 parts of acrylate monomer, 10-50 parts of phosphorus-containing flame-retardant monomer and 10-50 parts of sulfur-containing flame-retardant monomer; the raw materials are easy to obtain, the halogen-free flame retardant is safe, the synthetic process is simple, a highly toxic solvent is not adopted, and the green flame retardant aim can be achieved. The invention adopts the sulfur flame-retardant monomer containing sulfonate groups, which is different from the traditional phosphorus flame retardant, realizes phosphorus-sulfur flame-retardant synergy, and can form a more stable carbon layer at high temperature, thereby achieving the aim of more efficient flame retardance. The obtained composite coating has excellent light transmission, adhesion performance and mechanical performance, can be widely applied to the surfaces of various combustible base materials, and has the potential of industrial large-scale production and application.

Description

Phosphorus-sulfur synergistic flame-retardant composition, and preparation method and application thereof
Technical Field
The invention relates to the field of preparation of flame-retardant chemical materials, in particular to a phosphorus-sulfur synergistic flame-retardant composition, a preparation method and application thereof, and specifically relates to a phosphorus-sulfur synergistic flame-retardant copolymer coating capable of being adhered to the surface of a combustible substrate.
Background
The fire seriously threatens the safety of people's lives and properties because of the destructive and dangerous nature which is difficult to control. As combustible materials such as wood and polymers are increasingly used in daily life, improvement of the inherent combustibility of the materials is necessary.
The development and use of flame retardants are the most commonly used technical means in the past to improve the fire safety of materials. However, most of the flame retardants need to participate in the synthesis reaction of the matrix material or be introduced by a method such as internal mixer blending, and therefore, the defects that the flame retardants have limited applicability or seriously damage the inherent properties of the matrix material cannot be avoided. Therefore, constructing a coating layer with a flame-retardant function on the surface of a combustible substrate is an effective way to reduce the flammability without destroying the inherent properties.
The Chinese invention patent with publication number CN 11056936A discloses a self-flame-retardant antibacterial water-based polyester resin and a preparation method thereof, and the self-flame-retardant antibacterial water-based polyester resin comprises the following components in parts by weight: 6.0 to 12.0 portions of organic acid anhydride, 3.0 to 5.0 portions of carboxylic acid Schiff base, 3.0 to 8.0 portions of polybasic acid, 6.0 to 20.0 portions of polyol, 1.2 to 3.5 portions of 2-chloro-5-bromobenzoic acid, 1.5 to 3.5 portions of dimethylolpropionic acid, 2.0 to 5.0 portions of dimethylbenzene, 2.0 to 5.0 portions of neutralizer and 45.0 to 65.0 portions of deionized water. However, the halogen-based flame retardants have relatively low decomposition temperature and large smoke generation amount, and cause a large amount of smoke to suffocate people when fire occurs, so that increasingly stringent regulations have gradually extruded such flame retardants to the application market in consideration of environmental and health risks of the halogen-based flame retardants.
Chinese patent publication No. CN106833336A discloses a char-forming halogen-free environment-friendly flame-retardant coating, belonging to the technical field of flame-retardant materials. The flame retardant is a phosphorus flame retardant and a phosphorus-nitrogen flame retardant, and comprises the following components in parts by weight: 45-55 parts of adhesive, 20-25 parts of carbon forming agent, 15-20 parts of phosphorus flame retardant and 8-12 parts of phosphorus-nitrogen flame retardant. Although the environmental and health risks of halogen flame retardants are primarily solved, the fire protection requirements are higher and higher at present, and the stability of the carbon layer formed by the existing phosphorus flame retardants and coatings at high temperature is still insufficient.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the phosphorus-sulfur synergistic flame-retardant composition which has the advantages of simple synthesis process, greenness, no toxicity, good adhesiveness and flame retardance, good light transmittance, wide application prospect, capability of being popularized to the fields of buildings, bridges, pipelines, traffic and the like, capability of being tightly attached to the surfaces of various combustible substrates, capability of well keeping the inherent performance of a base material and capability of effectively reducing the combustible risk.
The purpose of the invention is realized by the following technical scheme: a phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 30-55 parts of a modifier;
phosphorus-containing flame retardant monomer: 10-50 parts;
sulfur-containing flame retardant monomer: 10-50 parts.
Further, the acrylic ester monomer comprises one or more of acrylic ester substances such as 2- [ [ (butylamino) carbonyl ] oxo ] ethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycidyl acrylate and the like.
Further, the phosphorus-containing flame retardant monomer includes one or more of 1-styryl phosphonic acid, ethylene phosphonic acid, phosphonic acid-BETA-styryl ester, dimethyl ethylene phosphonate, diethyl ethylene phosphonate, allyl diethyl phosphate and metal salt monomers thereof.
Further, the sulfur-containing flame retardant monomer comprises one or more of organic sulfonate substances such as sodium vinylsulfonate, sodium allylsulfonate, sodium styrene sulfonate, potassium styrene sulfonate, 2-ethylmethacrylate sodium salt, 3-propylmethacrylate potassium salt, methacryloyl ethyl sulfobetaine and the like.
Further, the molar part ratio of the phosphorus-containing flame-retardant monomer to the sulfur-containing flame-retardant monomer is 1.
The second purpose of the invention is to provide a preparation method of the phosphorus-sulfur synergistic flame-retardant composition. The second purpose of the invention is realized by the following technical scheme: a preparation method of a phosphorus-sulfur synergistic flame-retardant composition comprises the following steps:
A. mixing a phosphorus-containing flame-retardant monomer, a sulfur-containing flame-retardant monomer, an acrylate monomer and a solvent;
B. an initiator is added to the mixture.
Further, the solvent comprises one or more of water, dimethyl sulfoxide, ethanol, propanol, butanol or ethyl acetate;
the initiator comprises one or more of persulfate, azobisisobutyramidine hydrochloride, azobisisobutyronitrile, azobisisoheptonitrile and dibenzoyl peroxide.
Further, the step a specifically includes the following steps:
under the nitrogen atmosphere, adding a phosphorus-containing flame-retardant monomer, a sulfur-containing flame-retardant monomer and an acrylate monomer into a solvent for constant-temperature mixing;
the temperature of the solvent and the constant temperature are 60-80 ℃, and the total concentration of the phosphorus-containing flame-retardant monomer, the sulfur-containing flame-retardant monomer and the acrylate monomer solution is 10-50 wt%.
Further, the step B specifically includes the following steps:
adding an initiator into a mixture of a phosphorus-containing flame-retardant monomer, a sulfur-containing flame-retardant monomer, an acrylate monomer and a solvent mixture for the first time, carrying out constant-temperature copolymerization reaction, and adding the initiator for the second time before the reaction is finished to finally obtain a phosphorus-sulfur synergistic flame-retardant composition;
the time for adding the initiator for the first time is 30min and less after the phosphorus-containing flame-retardant monomer, the sulfur-containing flame-retardant monomer, the acrylate monomer and the solvent are mixed, the constant-temperature copolymerization reaction is carried out for 3-6 h after the initiator is added for the first time, and the time for adding the initiator for the second time is 0.5-1 h and less before the constant-temperature copolymerization reaction is finished;
the initiator dosage is 0.1-1.5 wt% of the total mass of the phosphorus-containing flame-retardant monomer, the sulfur-containing flame-retardant monomer and the acrylate monomer, the input amount of the initiator added for the first time is 80-95 wt% of the total dosage of the initiator, and the input amount of the initiator added for the second time is 5-20 wt% of the total dosage of the initiator.
The invention also aims to provide application of the phosphorus-sulfur synergistic flame-retardant composition. The third purpose of the invention is realized by the following technical scheme: use of a phosphorus-sulfur synergistic flame retardant composition for one or more of the outer surfaces of foam board, plastic, wood, metal substrates;
the phosphorus-sulfur synergistic flame-retardant composition is applied to the outer surface of a base material through one or more of dip coating, spray coating, brush coating, blade coating and roller coating processes and is cured; applying a thickness of at least 1 micron; preferably 1-3000 microns thick;
the curing conditions of the phosphorus-sulfur synergistic flame-retardant composition are 60-90 ℃ and 0.5-6 h.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) The comonomer raw materials in the phosphorus-sulfur synergistic flame-retardant composition comprise the following components in parts by mole: 30-55 parts of acrylate monomer, 10-50 parts of phosphorus-containing flame-retardant monomer and 10-50 parts of sulfur-containing flame-retardant monomer; the raw materials are easy to obtain, the halogen is safe, the synthetic process is simple, a highly toxic solvent is not adopted, and the green flame retardant target can be realized;
(2) The phosphorus-sulfur synergistic flame-retardant composition adopts the sulfur flame-retardant monomer containing sulfonate groups, and is different from the traditional phosphorus flame retardant, and a more stable carbon layer can be formed at high temperature, so that the aim of more efficient flame retardance is fulfilled;
(3) The phosphorus-sulfur synergistic flame-retardant composition has excellent light transmittance, adhesion performance and mechanical property, can be widely applied to the surfaces of various combustible base materials, and has the potential of industrial large-scale production and application.
Detailed Description
The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values are to be considered as specifically disclosed herein, the invention is described in detail below with reference to specific examples:
example 1
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a mixture;
phosphorus-containing flame retardant monomer: 30 parts of a binder;
sulfur-containing flame retardant monomer: 30 parts of the raw materials.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000041
A. vinyl Phosphonic Acid (VPA), sodium Allyl Sulfonate (AS) and hydroxyethyl methacrylate (HEMA) were weighed out and dissolved in an appropriate amount of solvent water under nitrogen atmosphere, the monomer feeding molar ratio was controlled to VPA/AS/HEMA = x/y/z, (x/y/z = 30/30/40), and the mixed solution was gradually warmed up to 65 ℃ with stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, a small amount of KPS is replenished again (the input amount is 0.2% of the total mass of the monomers), the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 30-AS30-HEMA 40).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The phosphorus-sulfur synergistic flame retardant composition Poly (VPA 30-AS30-HEMA 40) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94), and the test results are shown in Table 1.
Example 2
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 50 parts of a mixture;
phosphorus-containing flame retardant monomer: 25 parts of a binder;
sulfur-containing flame retardant monomers: and 25 parts of the total weight.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, which comprises the following steps:
Figure BDA0003927186030000051
A. vinyl Phosphonic Acid (VPA), sodium Allyl Sulfonate (AS) and hydroxyethyl methacrylate (HEMA) were weighed out and dissolved in an appropriate amount of solvent water under nitrogen atmosphere, the monomer feeding molar ratio was controlled to VPA/AS/HEMA = x/y/z, (x/y/z = 25/25/50), and the mixed solution was gradually warmed up to 65 ℃ with stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, a small amount of KPS is replenished again (the input amount is 0.2% of the total mass of the monomers), the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by dialysis according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 25-AS25-HEMA 50).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, blade coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferred thickness is between 1 and 3000 microns.
The weight average molecular weight and the heat release rate peak value (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) of the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 25-AS25-HEMA 50) are tested, and the test results are shown in Table 1.
Example 3
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a binder;
phosphorus-containing flame retardant monomer: 10 parts of a binder;
sulfur-containing flame retardant monomers: 50 parts of the components.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000061
A. vinyl Phosphonic Acid (VPA), sodium Allyl Sulfonate (AS) and hydroxyethyl methacrylate (HEMA) were weighed out and dissolved in an appropriate amount of solvent water under nitrogen atmosphere, the monomer feeding molar ratio was controlled to VPA/AS/HEMA = x/y/z, (x/y/z = 10/50/40), and the mixed solution was gradually warmed up to 65 ℃ with stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, a small amount of KPS is replenished again (the input amount is 0.2% of the total mass of the monomers), the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the using requirements, and the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 10-AS50-HEMA 40) is obtained.
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The weight average molecular weight and the heat release rate peak value (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) of the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 10-AS50-HEMA 40) are tested, and the test results are shown in Table 1.
Example 4
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a binder;
phosphorus-containing flame retardant monomer: 50 parts of a binder;
sulfur-containing flame retardant monomer: 10 parts.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000071
A. vinyl Phosphonic Acid (VPA), sodium Allyl Sulfonate (AS) and hydroxyethyl methacrylate (HEMA) were weighed out and dissolved in an appropriate amount of solvent water under nitrogen atmosphere, the monomer feeding molar ratio was controlled to VPA/AS/HEMA = x/y/z, (x/y/z = 50/10/40), and the mixed solution was gradually warmed up to 65 ℃ with stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, then a small amount of KPS (the input amount is 0.2% of the total mass of the monomers) is replenished again, the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by dialysis according to the use requirements, and the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 50-AS10-HEMA 40) is obtained.
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The weight average molecular weight and the heat release rate peak value (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) of the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 50-AS10-HEMA 40) are tested, and the test results are shown in Table 1.
Comparative example 1
A phosphorus-sulfur synergistic flame-retardant composition is different from the composition in example 1 in that the comonomer raw materials of the composition comprise the following components in parts by mole:
acrylate monomer: 60 parts;
phosphorus-containing flame retardant monomer: 20 parts of (1);
sulfur-containing flame retardant monomers: and 20 parts of the components.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000081
A. vinyl Phosphonic Acid (VPA), sodium Allyl Sulfonate (AS) and hydroxyethyl methacrylate (HEMA) were weighed out and dissolved in an appropriate amount of solvent water under nitrogen atmosphere, the monomer feeding molar ratio was controlled to VPA/AS/HEMA = x/y/z, (x/y/z = 20/20/60), and the mixed solution was gradually warmed up to 65 ℃ with stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, then a small amount of KPS (the input amount is 0.2% of the total mass of the monomers) is replenished again, the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the using requirements to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 20-AS20-HEMA 60).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, blade coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferred thickness is between 1 and 3000 microns.
The weight average molecular weight and the heat release rate peak value (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) of the phosphorus-sulfur synergistic flame-retardant composition Poly (VPA 20-AS20-HEMA 60) are tested, and the test results are shown in Table 1.
Example 5
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 30 parts of a binder;
phosphorus-containing flame retardant monomer: 35 parts of (B);
sulfur-containing flame retardant monomers: 35 parts of (A).
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000091
A. under the nitrogen atmosphere, 1-styryl phosphonic acid (PPA), sodium Vinyl Sulfonate (VS) and hydroxyethyl acrylate (HEA) are weighed and dissolved in a proper amount of solvent water, the monomer feeding molar ratio is controlled to be PPA/VS/HEA = x/y/z, (x/y/z = 35/35/30), and the mixed solution is gradually heated to 65 ℃ while stirring.
B. Then, a proper amount of initiator azodiisobutyramidine hydrochloride (AIBA) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8 percent of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25 percent, the constant temperature reaction is kept for 3h, a small amount of AIBA (the input amount is 0.2 percent of the total mass of the monomers) is replenished again, and the copolymer solution is taken out after the reaction is continuously carried out for 0.5 h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 35-VS35-HEA 30).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The weight average molecular weight of the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 35-VS35-HEA 30) and the heat release rate Peak (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) thereof were tested, and the test results are shown in Table 1.
Example 6
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a binder;
phosphorus-containing flame retardant monomer: 30 parts of a binder;
sulfur-containing flame retardant monomer: 30 parts of.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000101
A. 1-styrylphosphonic acid (PPA), sodium Vinylsulfonate (VS) and hydroxyethyl acrylate (HEA) are weighed out and dissolved in a suitable amount of solvent water under a nitrogen atmosphere, the monomer feeding molar ratio is controlled to PPA/VS/HEA = x/y/z, (x/y/z = 30/30/40), and the mixed solution is gradually heated to 65 ℃ while stirring is maintained.
B. Then, an appropriate amount of initiator azo-diisobutyronidine hydrochloride (AIBA) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8 percent of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25 percent, the constant temperature reaction is kept for 3h, a small amount of AIBA (the input amount is 0.2 percent of the total mass of the monomers) is replenished again, and the copolymer solution is taken out after the reaction is continued for 0.5 h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirements, and the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 30-VS30-HEA 40) is obtained.
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The weight average molecular weight of the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 30-VS30-HEA 40) and the Peak Heat Release Rate (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) thereof were tested, and the test results are shown in Table 1.
Example 7
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a mixture;
phosphorus-containing flame retardant monomer: 20 parts of (1);
sulfur-containing flame retardant monomer: 40 parts of the components.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, which comprises the following steps:
Figure BDA0003927186030000111
A. under the nitrogen atmosphere, 1-styryl phosphonic acid (PPA), sodium Vinyl Sulfonate (VS) and hydroxyethyl acrylate (HEA) are weighed and dissolved in a proper amount of solvent water, the monomer feeding molar ratio is controlled to PPA/VS/HEA = x/y/z, (x/y/z = 20/40/40), and the mixed solution is gradually heated to 65 ℃ while stirring.
B. Then, a proper amount of initiator azodiisobutyramidine hydrochloride (AIBA) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8 percent of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25 percent, the constant temperature reaction is kept for 3h, a small amount of AIBA (the input amount is 0.2 percent of the total mass of the monomers) is replenished again, and the copolymer solution is taken out after the reaction is continuously carried out for 0.5 h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 20-VS40-HEA 40).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The weight average molecular weight and the heat release rate peak value (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) of the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 20-VS40-HEA 40) are tested, and the test results are shown in Table 1.
Example 8
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a mixture;
phosphorus-containing flame retardant monomer: 40 parts of a binder;
sulfur-containing flame retardant monomers: and 20 parts of the components.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, which comprises the following steps:
Figure BDA0003927186030000121
A. under the nitrogen atmosphere, 1-styryl phosphonic acid (PPA), sodium Vinyl Sulfonate (VS) and hydroxyethyl acrylate (HEA) are weighed and dissolved in a proper amount of solvent water, the monomer feeding molar ratio is controlled to PPA/VS/HEA = x/y/z, (x/y/z = 40/20/40), and the mixed solution is gradually heated to 65 ℃ while stirring.
B. Then, a proper amount of initiator azodiisobutyramidine hydrochloride (AIBA) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8 percent of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25 percent, the constant temperature reaction is kept for 3h, a small amount of AIBA (the input amount is 0.2 percent of the total mass of the monomers) is replenished again, and the copolymer solution is taken out after the reaction is continuously carried out for 0.5 h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirements, and the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 40-VS20-HEA 40) is obtained.
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, blade coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferred thickness is between 1 and 3000 microns.
The weight average molecular weight and the heat release rate peak value (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) of the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 40-VS20-HEA 40) are tested, and the test results are shown in Table 1.
Comparative example 2
A phosphorus-sulfur synergistic flame-retardant composition is different from the composition in example 5 in that the comonomer raw materials of the composition comprise the following components in parts by mole:
acrylate monomer: 25 parts of a binder;
phosphorus-containing flame retardant monomer: 25 parts of a binder;
sulfur-containing flame retardant monomers: 50 parts of the components.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000131
A. under the nitrogen atmosphere, 1-styryl phosphonic acid (PPA), sodium Vinyl Sulfonate (VS) and hydroxyethyl acrylate (HEA) are weighed and dissolved in a proper amount of solvent water, the monomer feeding molar ratio is controlled to be PPA/VS/HEA = x/y/z, (x/y/z = 25/50/25), and the mixed solution is gradually heated to 65 ℃ while stirring.
B. Then, a proper amount of initiator azodiisobutyramidine hydrochloride (AIBA) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.8 percent of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25 percent, the constant temperature reaction is kept for 3h, a small amount of AIBA (the input amount is 0.2 percent of the total mass of the monomers) is replenished again, and the copolymer solution is taken out after the reaction is continuously carried out for 0.5 h. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 25-VS50-HEA 25).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, blade coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferred thickness is between 1 and 3000 microns.
The weight average molecular weight of the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 25-VS50-HEA 25) and the heat release rate Peak (PHRR), the oxygen index (LOI) and the vertical burning (UL-94) thereof were tested, and the test results are shown in Table 1.
Example 9
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 35 parts of (B);
phosphorus-containing flame retardant monomer: 35 parts of (B);
sulfur-containing flame retardant monomer: 30 parts of.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000141
A. under nitrogen atmosphere, 1-styrylphosphonic acid (PPA), 2-ethanesulfonate sodium methacrylate (SSEM) and hydroxypropyl methacrylate (HPMA) are weighed and dissolved in a proper amount of solvent water, the monomer feeding molar ratio is controlled to PPA/SSEM/HPMA = x/y/z, (x/y/z = 35/30/35), and the mixed solution is gradually heated to 70 ℃ while keeping stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.9% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, a small amount of KPS is replenished again (the input amount is 0.1% of the total mass of the monomers), the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 35-SSEM30-HPMA 35) is obtained.
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The phosphorus-sulfur synergistic flame retardant composition Poly (PPA 35-SSEM30-HPMA 35) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94) and the results are shown in Table 1.
Example 10
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a mixture;
phosphorus-containing flame retardant monomer: 30 parts of a binder;
sulfur-containing flame retardant monomer: 30 parts of.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000151
A. 1-styrylphosphonic acid (PPA), 2-ethanesulfonate sodium methacrylate (SSEM) and hydroxypropyl methacrylate (HPMA) are weighed and dissolved in an appropriate amount of solvent water under a nitrogen atmosphere, the monomer feeding molar ratio is controlled to PPA/SSEM/HPMA = x/y/z, (x/y/z = 30/30/40), and the mixed solution is gradually heated to 70 ℃ while keeping stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.9% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, a small amount of KPS is replenished again (the input amount is 0.1% of the total mass of the monomers), the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 30-SSEM30-HPMA 40).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The phosphorus-sulfur synergistic flame retardant composition Poly (PPA 30-SSEM30-HPMA 40) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94), and the results are shown in Table 1.
Example 11
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a binder;
phosphorus-containing flame retardant monomer: 20 parts of a binder;
sulfur-containing flame retardant monomers: 40 parts of the components.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, which comprises the following steps:
Figure BDA0003927186030000161
A. 1-styrylphosphonic acid (PPA), 2-ethanesulfonate sodium methacrylate (SSEM) and hydroxypropyl methacrylate (HPMA) are weighed and dissolved in an appropriate amount of solvent water under a nitrogen atmosphere, the monomer feeding molar ratio is controlled to PPA/SSEM/HPMA = x/y/z, (x/y/z = 20/40/40), and the mixed solution is gradually heated to 70 ℃ while keeping stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.9% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, then a small amount of KPS (the input amount is 0.1% of the total mass of the monomers) is replenished again, the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 20-SSEM40-HPMA 40).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The phosphorus-sulfur synergistic flame retardant composition Poly (PPA 20-SSEM40-HPMA 40) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94) and the results are shown in Table 1.
Example 12
A phosphorus-sulfur synergistic flame-retardant composition comprises the following components in parts by mole:
acrylate monomer: 40 parts of a mixture;
phosphorus-containing flame retardant monomer: 40 parts of a mixture;
sulfur-containing flame retardant monomers: and 20 parts.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000171
A. 1-styrylphosphonic acid (PPA), 2-ethanesulfonate sodium methacrylate (SSEM) and hydroxypropyl methacrylate (HPMA) are weighed and dissolved in an appropriate amount of solvent water under a nitrogen atmosphere, the monomer feeding molar ratio is controlled to PPA/SSEM/HPMA = x/y/z, (x/y/z = 40/20/40), and the mixed solution is gradually heated to 70 ℃ while keeping stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.9% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, then a small amount of KPS (the input amount is 0.1% of the total mass of the monomers) is replenished again, the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 40-SSEM20-HPMA 40).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The phosphorus-sulfur synergistic flame retardant composition Poly (PPA 40-SSEM20-HPMA 40) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94) and the results are shown in Table 1.
Comparative example 3
A phosphorus-sulfur synergistic flame retardant composition, which is different from the composition in example 9 in that the comonomer raw materials of the composition comprise the following components in parts by mole:
acrylate monomer: 25 parts of (1);
phosphorus-containing flame retardant monomer: 25 parts of (1);
sulfur-containing flame retardant monomers: 50 parts of the raw materials.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, which comprises the following steps:
Figure BDA0003927186030000181
A. under nitrogen atmosphere, 1-styrylphosphonic acid (PPA), 2-ethanesulfonate sodium methacrylate (SSEM) and hydroxypropyl methacrylate (HPMA) are weighed and dissolved in a proper amount of solvent water, the monomer feeding molar ratio is controlled to PPA/SSEM/HPMA = x/y/z, (x/y/z = 25/50/25), and the mixed solution is gradually heated to 70 ℃ while keeping stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.9% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, then a small amount of KPS (the input amount is 0.1% of the total mass of the monomers) is replenished again, the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement to obtain the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 25-SSEM50-HPMA 25).
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, knife coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferable thickness is between 1 and 3000 microns.
The phosphorus-sulfur synergistic flame retardant composition Poly (PPA 25-SSEM50-HPMA 25) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94) and the results are shown in Table 1.
Comparative example 4
A phosphorus-sulfur synergistic flame-retardant composition, which is different from the composition in example 9 in that the comonomer raw materials of the composition comprise the following components in parts by mole:
acrylate monomer: 60 parts;
phosphorus-containing flame retardant monomer: 15 parts of a mixture;
sulfur-containing flame retardant monomers: and 25 parts of the total weight.
In a specific embodiment, there is provided a method for preparing the phosphorus-sulfur synergistic flame-retardant composition, comprising the following steps:
Figure BDA0003927186030000191
A. 1-styrylphosphonic acid (PPA), 2-ethanesulfonate sodium methacrylate (SSEM) and hydroxypropyl methacrylate (HPMA) are weighed and dissolved in an appropriate amount of solvent water under a nitrogen atmosphere, the monomer feeding molar ratio is controlled to PPA/SSEM/HPMA = x/y/z, (x/y/z = 15/25/60), and the mixed solution is gradually heated to 70 ℃ while keeping stirring.
B. Then, an appropriate amount of initiator potassium persulfate (KPS) solution (1wt% in H2O) is measured, the effective component of the initiator is 0.9% of the total mass of the monomers, the initiator is slowly dripped into the solution at a constant speed within 0.5h, the mass percentage concentration of the monomers in the reaction system is controlled to be 20-25%, the constant temperature reaction is maintained for 3h, a small amount of KPS is replenished again (the input amount is 0.1% of the total mass of the monomers), the reaction is continued for 0.5h, and then the copolymer solution is taken out. Unreacted monomers and oligomers can be removed by a dialysis method according to the use requirement, and the phosphorus-sulfur synergistic flame-retardant composition Poly (PPA 15-SSEM25-HPMA 60) is obtained.
In a specific embodiment, the application of the phosphorus-sulfur synergistic flame-retardant composition is provided, wherein the phosphorus-sulfur synergistic flame-retardant composition is applied on the outer surface of a foamed sheet, plastic, wood or metal substrate through dip coating, spray coating, brush coating, blade coating and roller coating processes and is cured for 0.5 to 6 hours at the temperature of between 60 and 90 ℃, and the application thickness is at least 1 micron, and the preferred thickness is between 1 and 3000 microns.
The phosphorus-sulfur synergistic flame retardant composition Poly (PPA 15-SSEM25-HPMA 60) was tested for weight average molecular weight and its heat release rate Peak (PHRR), oxygen index (LOI), and vertical burn (UL-94) and the results are shown in Table 1.
TABLE 1 weight average molecular weight of phosphorus-sulfur synergistic flame retardant compositions and their Peak Heat Release Rate (PHRR), oxygen index (LOI) and vertical burn (UL-94) test results table
Figure BDA0003927186030000192
Figure BDA0003927186030000201
As can be seen from the examples in Table 1, the phosphorus-sulfur synergistic flame retardant copolymer coating Poly (VPAx-ASy-HEMAZ) prepared by the present invention passes the UL-94V-0 rating. However, too high a HEMA content can result in the copolymer coating popping up. In addition, the single excessively high sulfur-based flame retardant component or phosphorus-based flame retardant component is not as obvious in flame retardant synergy brought by the synergistic use of the two components in equal amount.
The phosphorus-sulfur synergistic flame-retardant copolymer coating Poly (PPAX-VSy-HEAZ) prepared by the invention can pass UL-94V-0 grade. However, too low an HMA content leads to difficulties in copolymerization and a decrease in molecular weight. The flame retardant synergy brought by the over-high single sulfur-based flame retardant component or phosphorus-based flame retardant component in the copolymer is not the same as that of the two components in the synergistic use.
The phosphorus-sulfur synergistic flame-retardant copolymer coating Poly (PPAX-SSEMy-HPMAz) prepared by the invention can pass the UL-94V-0 grade. Also, too high a HPMA content can lead to copolymer coating implosion, and too low a HPMA content can lead to difficult copolymerization and a decrease in molecular weight. The flame retardant synergy brought by the over-high single sulfur-based flame retardant component or phosphorus-based flame retardant component in the copolymer is not the same as that of the two components in the synergistic use.
The phosphorus-sulfur synergistic flame-retardant copolymer coating prepared by the invention can pass the UL-94V-0 grade, and shows extremely high limit oxygen index and low heat release rate far superior to that of the traditional high-molecular base material, so that the requirement of the phosphorus-sulfur synergistic flame-retardant copolymer coating as a surface fireproof coating of a combustible high-molecular material is met, the overall flame-retardant performance of the material is effectively improved, and the application of the phosphorus-sulfur synergistic flame-retardant copolymer coating in the scene of high fire safety requirement is widened. However, according to the actual measurement suggestion, the dosage of the acrylate film-forming monomer for synthesizing the phosphorus-sulfur synergistic flame-retardant copolymer coating is less than 60 percent so as to avoid the sudden polymerization of a copolymerization system; the total amount of the phosphorus-containing flame-retardant monomer and the sulfur-containing flame-retardant monomer is less than 75% to avoid the influence of too low polymerization degree of a system on use, and the suggested feeding proportion of the phosphorus-containing flame-retardant monomer and the sulfur-containing flame-retardant monomer is 1/1 to achieve the optimal flame retardance.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (10)

1. The phosphorus-sulfur synergistic flame-retardant composition is characterized in that the comonomer raw materials of the composition comprise the following components in parts by mole:
acrylate monomer: 30-55 parts of a modifier;
phosphorus-containing flame retardant monomer: 10-50 parts;
sulfur-containing flame retardant monomers: 10-50 parts.
2. The phosphorous-sulfur synergistic flame retardant composition of claim 1, wherein the acrylate monomers comprise one or more of 2- [ [ (butylamino) carbonyl ] oxo ] ethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, glycidyl acrylate and the like acrylates.
3. The phosphorus-sulfur synergistic flame retardant composition of claim 1, wherein the phosphorus-containing flame retardant monomer comprises one or more of 1-styrylphosphonic acid, vinylphosphonic acid, phosphonic acid-BETA-styryl ester, dimethyl vinylphosphonate, diethyl vinylphosphonate, allyl diethyl phosphate, and metal salt monomers thereof.
4. The phosphorous-sulfur synergistic flame retardant composition of claim 1, wherein the sulfur-containing flame retardant monomer comprises one or more of organic sulfonate species such as sodium vinyl sulfonate, sodium allyl sulfonate, sodium styrene sulfonate, potassium styrene sulfonate, 2-ethanesulfonate sodium methacrylate, 3-propyl methacrylate potassium sulfonate, methacrylethyl sulfobetaine, and the like.
5. The phosphorus-sulfur synergistic flame retardant composition of claim 1, wherein the molar part ratio of the phosphorus-containing flame retardant monomer to the sulfur-containing flame retardant monomer is 1.
6. A method for preparing the phosphorus-sulfur synergistic flame retardant composition according to any one of claims 1 to 5, comprising the steps of:
A. mixing a phosphorus-containing flame-retardant monomer, a sulfur-containing flame-retardant monomer, an acrylate monomer and a solvent;
B. an initiator is added to the mixture.
7. The method of preparing a phosphorus-sulfur synergistic flame retardant composition of claim 6, wherein the solvent comprises one or more of water, dimethylsulfoxide, ethanol, propanol, butanol, or ethyl acetate;
the initiator comprises one or more of persulfate, azobisisobutyramidine hydrochloride, azobisisobutyronitrile, azobisisoheptonitrile and dibenzoyl peroxide.
8. The method for preparing the phosphorus-sulfur synergistic flame-retardant composition according to claim 6, wherein the step A specifically comprises the following steps:
under the nitrogen atmosphere, adding a phosphorus-containing flame-retardant monomer, a sulfur-containing flame-retardant monomer and an acrylate monomer into a solvent for constant-temperature mixing;
the temperature of the solvent and the constant temperature are 60-80 ℃, and the total concentration of the phosphorus-containing flame-retardant monomer, the sulfur-containing flame-retardant monomer and the acrylic ester monomer solution is 10-50 wt%.
9. The method for preparing the phosphorus-sulfur synergistic flame retardant composition according to claim 6, wherein the step B comprises the following steps:
adding an initiator into a mixture of a phosphorus-containing flame-retardant monomer, a sulfur-containing flame-retardant monomer, an acrylate monomer and a solvent mixture for the first time, carrying out constant-temperature copolymerization reaction, and adding the initiator for the second time before the reaction is finished to finally obtain a phosphorus-sulfur synergistic flame-retardant composition;
the time for adding the initiator for the first time is 30min and less after the phosphorus-containing flame-retardant monomer, the sulfur-containing flame-retardant monomer, the acrylate monomer and the solvent are mixed, the constant-temperature copolymerization reaction is carried out for 3-6 h after the initiator is added for the first time, and the time for adding the initiator for the second time is 0.5-1 h and less before the constant-temperature copolymerization reaction is finished;
the dosage of the initiator is 0.1-1.5 wt% of the total mass of the phosphorus-containing flame-retardant monomer, the sulfur-containing flame-retardant monomer and the acrylate monomer, the dosage of the initiator added for the first time is 80-95 wt% of the total dosage of the initiator, and the dosage of the initiator added for the second time is 5-20 wt% of the total dosage of the initiator.
10. Use of a phosphorus-sulfur synergistic flame retardant composition according to any one of claims 1 to 5, wherein the phosphorus-sulfur synergistic flame retardant composition is used on the outer surface of one or more substrates of foam board, plastic, wood and metal;
the phosphorus-sulfur synergistic flame-retardant composition is applied to the outer surface of a base material through one or more of dip coating, spray coating, brush coating, blade coating and roller coating processes and is cured; applying a thickness of at least 1 micron;
the curing conditions of the phosphorus-sulfur synergistic flame-retardant composition are 60-90 ℃ and 0.5-6 h.
CN202211377923.XA 2022-11-04 2022-11-04 Phosphorus-sulfur synergistic flame-retardant composition, and preparation method and application thereof Pending CN115594792A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090306297A1 (en) * 2006-01-26 2009-12-10 Centre National De La Recherche Scientifique Process for preparing a copolymer with controlled architecture, of telomer or block copolymer type, obtained from vinyl phosphonate monomers, by iodine transfer polymerization
CN109232785A (en) * 2018-08-06 2019-01-18 台启龙 Flame-retardant polypropelene acid esters lotion and preparation method thereof
CN109575552A (en) * 2017-09-29 2019-04-05 中国石油化工股份有限公司 Functional flame-retardant high-molecular composition and its preparation method and application
CN109610191A (en) * 2018-11-20 2019-04-12 武汉纺织大学 A kind of preparation method of organic/inorganic composite flame-proof cotton fabric coating

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090306297A1 (en) * 2006-01-26 2009-12-10 Centre National De La Recherche Scientifique Process for preparing a copolymer with controlled architecture, of telomer or block copolymer type, obtained from vinyl phosphonate monomers, by iodine transfer polymerization
CN109575552A (en) * 2017-09-29 2019-04-05 中国石油化工股份有限公司 Functional flame-retardant high-molecular composition and its preparation method and application
CN109232785A (en) * 2018-08-06 2019-01-18 台启龙 Flame-retardant polypropelene acid esters lotion and preparation method thereof
CN109610191A (en) * 2018-11-20 2019-04-12 武汉纺织大学 A kind of preparation method of organic/inorganic composite flame-proof cotton fabric coating

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