CN112480323A - Polystyrene flame-retardant material and preparation method and application thereof - Google Patents
Polystyrene flame-retardant material and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic linkage)
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2475—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aralkylamines
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
Abstract
The invention provides a polystyrene flame-retardant material and a preparation method and application thereof, wherein the preparation raw materials of the polystyrene flame-retardant material comprise styrene, a reactive phosphorus-containing flame retardant, toughened rubber and an initiator, and the reactive phosphorus-containing flame retardant has a structure shown in a formula I or a formula II and contains an ethylene group; the reactive phosphorus-containing flame retardant and styrene jointly serve as monomers to participate in free radical polymerization reaction, and finally exist in polystyrene in a molecular chain fragment form, so that the phenomena of micromolecule precipitation, water dissolution or hydrolysis are avoided, and efficient and stable environment-friendly flame retardance is really realized. The polystyrene flame-retardant material provided by the invention has excellent flame-retardant property and mechanical property, and the preparation process is simple, so that the polystyrene flame-retardant material has a wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polystyrene flame retardant material, and a preparation method and application thereof.
Background
Polystyrene (abbreviated as PS) is one of five general-purpose synthetic resins, and is a polymer formed by radical polymerization of styrene monomers. The general polystyrene is a homopolymer of styrene, has a molecular weight of about 5-30 ten thousand, a glass transition temperature of 95 ℃, and side groups of macromolecular chains of the general polystyrene are benzene rings, and the random arrangement of the benzene rings determines that the general polystyrene is a typical hard plastic, is light in transparent color, good in fluidity, easy to process and mold, and good in electrical property, but has the defects of brittleness, solvent resistance, ultraviolet light and oxygen resistance, elongation of only 1-3%, and the like. In order to improve the brittleness problem of general polystyrene, people graft-copolymerize styrene monomer and butadiene rubber to obtain high impact polystyrene (HIPS for short), and a two-phase system is formed by a rubber phase and a polystyrene phase, so that the toughness and impact resistance of the polystyrene are greatly improved, and the polystyrene is widely applied to lining and shell materials of electric elements, household appliances, office equipment, automobile parts and the like.
Polystyrene materials are generally inflammable, the limit oxygen index of the polystyrene materials is only about 18%, the polystyrene materials can be continuously combusted after leaving a fire source, the heat release amount is large, the smoke generation amount is large, and toxic gases are released. In order to improve the safety of polystyrene in use, polystyrene must be flame-retardant modified.
CN102219929A discloses a modified magnesium hydroxide flame retardant, a high impact polystyrene composite flame retardant material composed of the same and a preparation method thereof, wherein the modified magnesium hydroxide flame retardant has an average particle size of 1-100 mu m and a BET specific surface area of 0.5-20 m2The magnesium hydroxide powder/g is obtained by surface treatment of sulfonated high impact polystyrene, the high impact polystyrene composite flame retardant material comprises high impact polystyrene, the modified magnesium hydroxide flame retardant and other common additives of polystyrene, the composite flame retardant material has good tensile strength, bending strength and impact strength, the flame retardance is excellent, and the oxygen index can reach 29%.
CN100372886C discloses a flame-retardant polystyrene composition and a preparation method thereof, wherein the composition comprises 100 parts by weight of polystyrene, 8-25 parts by weight of halogenated flame retardant and 2-6 parts by weight of synergistic flame retardant; wherein the halogen flame retardant is a mixture of decabromodiphenylethane and heat-stable hexabromocyclododecane, the mixing ratio of the decabromodiphenylethane and the heat-stable hexabromocyclododecane is 2: 1-1: 2, and the synergistic flame retardant is antimony trioxide. The flame-retardant polystyrene composition prepared by melting and blending the components has good flame retardant performance, the flame retardant level can reach FV-0 level, the oxygen index can reach 28 percent, and the flame-retardant polystyrene composition is suitable for various severe environments.
CN108178883A discloses a halogen-free flame-retardant polystyrene with selectively distributed flame retardant and a preparation method thereof, wherein the halogen-free flame-retardant polystyrene is prepared from polystyrene, a flame retardant, a char-forming agent and a flame-retardant synergist under a hot-pressing process, wherein the flame retardant is one or a mixture of more of ammonium polyphosphate, ammonium phosphate or melamine phosphate, the char-forming agent is one or a mixture of more of pentaerythritol, dipentaerythritol or phenolic resin, and the flame-retardant synergist is carbon materials such as graphene, nano graphite micro-sheets and nano graphite powder; the halogen-free flame-retardant polystyrene is low in flame retardant consumption and good in flame retardant effect, and the limited oxygen index is 28-37%.
However, in the prior art, the flame retardant efficiency of inorganic flame retardants such as magnesium hydroxide and graphite is low, and a large amount of inorganic flame retardants are required to be added to realize a good flame retardant effect, but the mechanical properties of the material are affected by the addition of a large amount of inorganic filler; although the flame retardant substance containing halogen such as bromine has excellent flame retardant property, dioxin and other products which are difficult to degrade are generated during combustion, so that serious environmental pollution is caused, and the human health is harmed; although the combustion products of the additive phosphorus-nitrogen halogen-free flame retardant material cannot cause environmental pollution, molecules, decomposition products or water-soluble substances of the additive phosphorus-nitrogen halogen-free flame retardant material can enter the environment and pollute the environment due to the migration property and precipitation property in the processes of production, storage, use and scrapping treatment, and most additive flame retardants are easy to hydrolyze and the like, so that the real environment-friendly flame retardant cannot be realized.
Therefore, it is a research focus in the field to develop a high-performance polystyrene material that can really achieve safety, environmental protection and flame retardance to meet the application requirements.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polystyrene flame-retardant material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a polystyrene flame retardant material, and the preparation raw materials of the polystyrene flame retardant material comprise styrene, a reactive phosphorus-containing flame retardant, toughened rubber and an initiator.
The reactive phosphorus-containing flame retardant has a structure shown in a formula I or a formula II:
wherein L is1、L2Each independently selected from the group containing terminal vinyl groups.
Z1、Z2Each independently selected from phosphorus-containing groups.
M1Selected from linear alkylene, branched alkylene or arylene.
M2Selected from any organic group that satisfies the chemical environment.
Y1、Y2Each independently selected from an inert group, -OH, a sulfur atom, an oxygen atom, or-H.
X1Selected from any organylene group that satisfies a chemical environment.
X2And the aliphatic group containing carbon-carbon double bonds is selected from C2-C30.
a. b, c, d, f, g, h are each independently selected from integers of 0 to 5, such as 0, 1, 2, 3, 4 or 5; and a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and b + c + h ≦ 5 (e.g., b + c + h ≦ 0, 1, 2, 3, 4, or 5) and a + d + g ≦ 5 (e.g., a + d + g ≦ 0, 1, 2, 3, 4, or 5).
e is an integer from 0 to 100, such as 0, 1, 3, 5, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, and the specific values therebetween are not exhaustive for the purpose of space and brevity.
The polystyrene flame-retardant material provided by the invention comprises the preparation raw materials of styrene, toughened rubber, a flame retardant and an initiator, wherein the flame retardant is a reactive phosphorus-containing flame retardant containing carbon-carbon double bonds. In the preparation process of the polystyrene flame retardant material, carbon-carbon double bonds in the reactive phosphorus-containing flame retardant and double bonds in styrene generate free radicals under the initiation of an initiator and jointly generate free radical polymerization, so that a flame retardant group is embedded into a macromolecular structure of polystyrene through a stable chemical bond to realize the flame retardant modification of polystyrene resin; when styrene and a flame retardant containing a carbon-carbon double bond are copolymerized, part of free radicals are transferred to rubber chains to generate grafting points, and the styrene is polymerized at the grafting points to form branched chains, so that the graft copolymer is obtained. Therefore, in the polystyrene flame-retardant material provided by the invention, the flame retardant is used as a polymerization monomer to participate in a free radical polymerization reaction during the synthesis of the polystyrene resin, and finally exists in the polystyrene resin in the form of molecular chain fragments, so that the phenomenon of small molecule precipitation is avoided, and the phenomenon that an additive type flame retardant is easily dissolved in water to precipitate or is hydrolyzed is also avoided, so that the polystyrene flame-retardant material provided by the invention can really realize a high-efficiency environment-friendly flame-retardant effect; more importantly, the flame retardant group is introduced into the polymer in a chemical bond mode through copolymerization, micro-phase separation caused by physical blending in the process of additive flame retardant modification is avoided, the mechanical property of the polystyrene is not influenced, and the polystyrene can be reinforced and toughened to a certain extent through the molecular structure of the reactive phosphorus-containing flame retardant.
Preferably, the preparation raw materials of the polystyrene flame-retardant material comprise the following components:
in the present invention, the styrene may be used in an amount of 61 parts by weight, 63 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 85 parts by weight, 88 parts by weight, 90 parts by weight, 95 parts by weight or 98 parts by weight, and specific points therebetween, and the present invention is not exhaustive and for the sake of brevity and clarity, and the specific points included in the range are not included.
In the present invention, the reactive phosphorus-containing flame retardant may be used in an amount of 4 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, and specific points therebetween, which are not exhaustive for the purpose of brevity and clarity.
In the present invention, the toughening rubber may be used in an amount of 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 parts by weight, and specific values therebetween are not exhaustive for the sake of brevity and simplicity.
In the present invention, the initiator may be used in an amount of 0.02 parts by weight, 0.04 parts by weight, 0.06 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight or 0.45 parts by weight, and specific values therebetween, and the present invention is not exhaustive and for the sake of brevity only, specific values included in the range are not intended.
Preferably, said L1、L2Each independently selected from
Wherein j is an integer of 0 to 20 (e.g., 0, 1, 2, 3, 5, 6, 8, 10, 12, 13, 15, 16, 18, or 20, etc.), and R is10Is an alkyl group of C1 to C10 (e.g., C2, C3, C4, C5, C6, C7, C8 or C9), and # represents an access position of the group.
Preferably, Z is1、Z2Each independently selected from
One of (1), R1Is selected from any one of saturated or unsaturated alkyl, aryl or heteroaryl, and is more preferably methyl, ethyl or phenyl.
Preferably, said M1Selected from C, N,
O、-O-RT-, one of C1-C30 straight chain or branched chain alkylene, C6-C30 arylene or C5-C7 heteroarylene; further preferred is
-O-RT-, C1-C5 straight chain alkylene, C3-C5 branched chain alkylene, phenyl or naphthyl; more preferably a C1-C3 linear alkylene group, a C3 branched alkylene group, a phenyl group or a naphthyl group; wherein R isTIs one selected from C1-C10 straight chain or branched chain alkyl and C6-C30 aryl.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
The C1-C5 linear alkylene comprises methylene, ethylene, propylene, butylene or pentylene.
The C3-C5 branched chain alkylene group comprises C3, C4 or C5 branched chain alkylene group.
The C1-C10 include C2, C3, C5, C7, C9 and the like.
Preferably, said M2Selected from C, N,
O、-O-RT-, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
One of (1); wherein R isTSelected from one of C1-C10 straight chain or branched chain alkyl and C6-C30 aryl, R2-R9Each independently selected from one of C1-C10 straight chain or branched chain alkylene, L2、Y2、Z2Is connected to R2-R9N, m, i, k are each independently selected from integers of 0 to 100, such as 0, 1, 3, 5, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 95, and the specific values therebetween, are not intended to be exhaustive or to limit the invention to the specific values encompassed by the scope, for reasons of brevity and clarity.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
The C1-C10 comprise C2, C3, C4, C5, C6, C7, C8 or C9.
Preferably, said R is2-R9Each independently selected from one of C1-C6 linear or branched chain alkylene groups, such as C1, C2, C3, C4, C5 or C6 linear or branched chain alkylene groups.
Preferably, n, m, i, k are each independently selected from integers of 0 to 30, such as 0, 1, 3, 5, 8, 10, 15, 20, 25 or 29, and specific values therebetween, not to mention space and for brevity, the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, said Y is1、Y2Each independently selected from-H, -OH, or ═ O.
Preferably, said X1Selected from N, S, substituted or unsubstituted C1-C30 straight or branched chain alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C7 heteroarylene, substituted or unsubstituted C1-C30 alkyleneamino, substituted or unsubstituted C1-C30 alkyleneaminoAcyl, substituted or unsubstituted C1-C30 alkylene ester group, substituted or unsubstituted C6-C30 arylene amine group, substituted or unsubstituted C6-C30 arylene acyl group or C6-C30 arylene ester group, more preferably one of substituted or unsubstituted C1-C5 straight chain or branched alkylene group, substituted or unsubstituted C1-C5 alkylene amine group, substituted or unsubstituted C1-C5 alkylene acyl group, and substituted or unsubstituted C1-C5 alkylene ester group, and still more preferably-NH-R-, -R '-NH-, -R' -O-, -R "-V-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", R ″VEach independently selected from substituted or unsubstituted C1 to C10 straight or branched chain alkylene.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring. By "stable compound" is meant a compound that can be isolated from a reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
The C1-C5 comprise C1, C2, C3, C4 or C5.
The C1-C10 comprise C2, C3, C4, C5, C6, C7, C8 or C9.
Preferably, said X2Is composed of
Wherein R isq、RsEach independently selected from a single bond or one of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) alkylene.
Preferably, the reactive phosphorus-containing flame retardant has a structure as shown in formula III, formula IV, formula V, formula VI, formula VII, or formula VIII:
wherein L is1、L2Each independently selected from
Wherein j is an integer of 0 to 3 (e.g., 1 or 2), R10Is C1-C3 (such as C1, C2 or C3) alkyl, # represents the access position of the group.
M1Is selected from
-O-RT-, C1-C3 (for example, C1, C2 or C3) straight chain alkylene, C3 branched chain alkylene, naphthyl or phenyl.
M2Selected from C, N,
O、-O-RTLinear or branched alkyl of-C1 to C6 (e.g. C2, C3, C4, C5 or C6),
Wherein R isTIs one of C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkyl, phenyl or biphenyl, R2-R9Each is independentSelected from C1-C6 (e.g., C1, C2, C3, C4, C5, or C6) straight or branched chain alkylene, n, m, i, k are each independently selected from integers of 0-30, e.g., 0, 1, 3, 5, 8, 10, 15, 20, 25, or 29, and the specific values therebetween are not exhaustive and for brevity, the invention is not intended to be limited to the specific values encompassed by the stated ranges.
L2、Y2、Z2Is connected to R2-R9Any connectable location of (a).
R1Is methyl or ethyl.
R、R'、R”、RV、RPEach independently selected from substituted or unsubstituted C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched chain alkylene.
Rq、RsEach independently selected from a single bond or a C1-C3 (e.g., C1, C2, or C3) alkylene group.
Y1、Y2Each independently selected from-H, -OH or ═ O.
a. b, g and h are respectively and independently selected from 0, 1 or 2, a + b is not less than 2, f and g are not 0 at the same time, and g and h are not 0 at the same time.
e is an integer from 0 to 20, such as 0, 1, 3, 5, 8, 10, 13, 15, 18, or 19, and the specific values therebetween are not exhaustive for the invention and for brevity.
f is 0 or 1.
Preferably, the reactive phosphorus-containing flame retardant is further preferably any one of or a combination of at least two of the compounds having the following structures:
wherein R isPOne selected from substituted or unsubstituted C1-C8 (e.g., C2, C3, C4, C5, C6, C7, or C8) straight chain or branched chain alkylene; r1Is methyl or ethyl; e is 0 to 5 (e.g., 0, 1, 2, 3, 4)Or 5) is used.
Preferably, the toughening rubber is cis-1, 4-polybutadiene rubber and/or styrene-butadiene rubber, and is further preferably cis-1, 4-polybutadiene rubber.
Preferably, the cis-1, 4-polybutadiene rubber includes a low cis-1, 4-polybutadiene rubber and a high cis-1, 4-polybutadiene rubber.
Preferably, the initiator is a peroxide initiator.
Preferably, the peroxide initiator is selected from one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide or tert-butyl peroxybenzoate.
Preferably, the raw materials for preparing the polystyrene flame-retardant material also comprise an organic solvent.
Preferably, the organic solvent is ethylbenzene.
Preferably, the amount of ethylbenzene added is 18-23% of the mass of styrene, for example 18.5%, 19%, 20%, 20.5%, 21%, 22% or 23%, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range, and more preferably 20%.
In another aspect, the present invention provides a method for preparing a polystyrene flame retardant material as described above, comprising the steps of: mixing styrene, a reactive phosphorus-containing flame retardant, a toughening rubber and an initiator, and carrying out bulk graft polymerization to obtain the polystyrene flame retardant material.
Preferably, the reaction temperature of the bulk graft polymerization is 80 to 230 ℃, such as 82 ℃, 84 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 95 ℃, 98 ℃, 100 ℃, 103 ℃, 105 ℃, 108 ℃, 110 ℃, 120 ℃, 125 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃ or 225 ℃, and specific values therebetween are not limited in space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the reaction time of the bulk graft polymerization is 7 to 20 hours, such as 8 hours, 9 hours, 10 hours, 12 hours, 14 hours, 15 hours, 16 hours, 17 hours or 19 hours, and specific values therebetween, which are not limited by space and for the sake of brevity, are not exhaustive.
Preferably, the bulk graft polymerization is carried out under stirring conditions.
Preferably, the bulk graft polymerization is carried out in a protective atmosphere.
Preferably, the protective atmosphere is nitrogen or argon.
Preferably, the preparation method also comprises the post-treatment of the product.
Preferably, the post-treatment is performed by means of a devolatilization device.
Preferably, the preparation method specifically comprises the following steps: under the protection of nitrogen, mixing styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and an organic solvent, stirring and reacting for 7-20 h at the temperature of 80-230 ℃, and stopping reaction; and removing residual styrene and organic solvent by using a devolatilization device to obtain the polystyrene flame-retardant material.
In another aspect, the invention provides an application of the polystyrene flame retardant material in the shells, linings and automobile parts of electronic and electric appliances.
Compared with the prior art, the invention has the following beneficial effects:
the raw materials for preparing the polystyrene flame-retardant material comprise styrene, a reactive phosphorus-containing flame retardant, toughened rubber and an initiator, wherein the reactive phosphorus-containing flame retardant contains vinyl and can generate free radical copolymerization with a styrene monomer, so that the flame retardant exists in polystyrene resin in a molecular chain fragment form finally, the phenomenon of micromolecule precipitation is avoided, the phenomenon that some additive flame retardants are easily dissolved in water to precipitate or hydrolyze is also avoided, and efficient environment-friendly flame retardance is really realized; and the reactive phosphorus-containing flame retardant has certain reinforcing and toughening effects on the polystyrene flame-retardant material. The combustibility of the polystyrene flame-retardant material can reach V-0 level, the combustibility is still V-0 level after water boiling,high hardness, toughness and impact strength, the tensile strength can reach more than 41MPa, the elongation at break is 47.9-53%, and the impact strength reaches 8.5KJ/m2The flame retardant has excellent flame retardance, flame retardant stability and mechanical properties, and has the advantages of simple preparation process, easily obtained raw materials and wide industrial application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of 4-aminostyrene, 2.2mol of dimethyl hydroxymethyl phosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 500mL of ethanol into a reaction kettle, stirring and heating until the ethanol flows back; then continuously reacting for 24 hours under the stirring condition; and (4) after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1H NMR(CDCl3400MHz, TMS): δ 6.57-6.69,7.13-7.26(m,4H, H on the phenyl ring), 6.61-6.70(t,1H, ═ CH-),5.69-5.75(d,1H, CH-)2H) 5.11 to 5.23(d,1H, CH)2H) 3.57-3.71(d,12H, -CH)3)。
Preparation example 2
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of N-methyl-3-phenyl-2-propylene-1-amine, 1.2mol of diethyl hydroxymethyl phosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 400mL of ethanol into a reaction kettle, and stirring and heating until the ethanol flows back; then continuously reacting for 24 hours under the stirring condition; and (4) after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1H NMR(CDCl3400MHz, TMS): δ 7.01-7.19(m,5H, H on the phenyl ring), 6.42-6.55(d,1H, ═ CH-),6.08-6.14(m,1H, ═ CH-),1.27(t,6H, -CH-)3)。
Preparation example 3
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of 4-aminostilbene, 2.2mol of hydroxymethyl dimethyl phosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 500mL of ethanol into a reaction kettle, stirring and heating until the ethanol flows back; then continuously reacting for 24 hours under the stirring condition; and (4) after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1H NMR(CDCl3400MHz, TMS): δ 7.23-7.61,6.67-6.73(m,7H, H on the phenyl ring), 6.74-6.81(d,2H, ═ CH-),3.55-3.71(d,12H, — CH-),3.55-3.713)。
Preparation example 4
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
1mol of maleic anhydride, 2.1mol of dimethyl hydroxymethylphosphite, 500mL of cyclohexane and 0.3mol of NaHSO4·H2Adding O into a reaction kettle, heating to 120 ℃, refluxing and reacting for 6h under stirring, adding saturated sodium carbonate solution after the reaction is finished, extracting, stirring for 20min, separating out an organic phase by using a separating funnel, and distilling under reduced pressure to remove the solvent to obtain the targetAnd (3) obtaining the product.
1H NMR(CDCl3,400MHz,TMS):δ6.89-7.01(s,4H,-CH2-),6.35-6.52(d,2H,-CH＝CH-),3.42-3.58(d,12H,-CH3)。
Preparation example 5
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of maleimide, 1.2mol of diethyl hydroxymethyl phosphite, 0.1g of DMAP, 0.1mol of sodium hydroxide and 500mL of ethanol into a reaction kettle, stirring and heating until the ethanol flows back, then continuing to react for 24h under stirring, washing with water to be neutral after the reaction is finished, and removing impurities to obtain a target product.
1H NMR(CDCl3,400MHz,TMS):δ6.98-7.05(s,2H,-CH＝CH-),3.73-3.86(m,4H,-CH2-),1.24(t,6H,-CH3)。
Preparation example 6
A reactive phosphorus-containing flame retardant with vinyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of 4-aminostyrene, 2.2mol of diethyl hydroxymethyl phosphite, 0.1mol of sodium hydroxide, 0.1g of DMAP and 500mL of ethanol into a reaction kettle, stirring and heating until the ethanol flows back; then continuously reacting for 24 hours under the stirring condition; and (4) after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1H NMR(CDCl3400MHz, TMS): δ 6.44-6.51,7.08-7.15(m,4H, H on the phenyl ring), 6.57-6.68(t,1H, ═ CH-),5.64-5.71(d,1H, CH-)2H) 5.18-5.29(d,1H, CH)2H) 3.42-3.59(m,12H, -CH)2-),1.21(t,12H,-CH3)。
Examples 1 to 6
The polystyrene flame-retardant material comprises the following raw materials in parts by weight:
wherein the reactive phosphorus-containing flame retardants provided in preparation examples 1-6 are reactive phosphorus-containing flame retardants with vinyl groups, the toughening rubber is low cis-1, 4-polybutadiene rubber (SKD-L), and the initiator is dibenzoyl peroxide (BPO); in order to avoid the excessive high viscosity and facilitate stirring and heat transfer, 15 parts by weight of ethylbenzene is also added as a solvent in the preparation.
The preparation method comprises the following steps:
(1) adding styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and ethylbenzene into reaction equipment, stirring and heating under the protection of nitrogen, and stirring and reacting for 5 hours at 90 ℃; then heating to 120 ℃, continuously stirring for reaction for 5 hours, and stopping the reaction;
(2) transferring the product obtained in the step (1) into a devolatilization device, removing residual styrene monomer and solvent, and enabling the content of residual styrene to be lower than 2.5% to obtain the polystyrene flame-retardant material.
Example 7
The embodiment provides a polystyrene flame-retardant material, which comprises the following components in parts by weight:
wherein the reactive phosphorus-containing flame retardants are the reactive phosphorus-containing flame retardants with vinyl groups provided in preparation example 1, the toughening rubber is low cis-1, 4-polybutadiene rubber (SKD-L), and the initiator is BPO; in order to avoid the excessive high viscosity and facilitate stirring and heat transfer, 12 parts by weight of ethylbenzene is also added as a solvent in the preparation.
The preparation method comprises the following steps:
(1) adding styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and ethylbenzene into reaction equipment, stirring and heating under the protection of nitrogen, and stirring and reacting for 7 hours at 85 ℃; then heating to 125 ℃, continuously stirring for reaction for 5 hours, and stopping the reaction;
(2) transferring the product obtained in the step (1) into a devolatilization device, removing residual styrene monomer and solvent, and enabling the content of residual styrene to be lower than 2.5% to obtain the polystyrene flame-retardant material.
Example 8
The embodiment provides a polystyrene flame-retardant material, which comprises the following components in parts by weight:
wherein the reactive phosphorus-containing flame retardants are the reactive phosphorus-containing flame retardants with vinyl groups provided in preparation example 1, the toughening rubber is low cis-1, 4-polybutadiene rubber (SKD-L), and the initiator is BPO; in order to avoid the excessive viscosity and facilitate stirring and heat transfer, 20 parts by weight of ethylbenzene is also added as a solvent in the preparation process.
The preparation method comprises the following steps:
(1) adding styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and ethylbenzene into reaction equipment, stirring and heating under the protection of nitrogen, and stirring and reacting for 4 hours at 95 ℃; then heating to 130 ℃, continuously stirring for reaction for 5.5h, and stopping the reaction;
(2) transferring the product obtained in the step (1) into a devolatilization device, removing residual styrene monomer and solvent, and enabling the content of residual styrene to be lower than 2.5% to obtain the polystyrene flame-retardant material.
Comparative example 1
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with an equal part by weight of styrene.
Comparative example 2
This comparative example is different from example 1 in that ammonium polyphosphate is substituted for the reactive phosphorus-containing flame retardant in equal parts by weight.
Comparative example 3
This comparative example differs from example 1 in that triphenyl phosphate is substituted for the reactive phosphorus-containing flame retardant and the like in parts by weight.
Comparative example 4
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with 45 parts by weight of ammonium polyphosphate.
Comparative example 5
This comparative example is different from example 1 in that the reactive phosphorus-containing flame retardant was 2 parts by weight.
Comparative example 6
This comparative example is different from example 1 in that the reactive phosphorus-containing flame retardant was 43 parts by weight.
And (3) performance testing:
(1) tensile strength, elongation at break: testing by using a GMT4503 type microcomputer control electronic universal testing machine according to the standard regulation of GB/T1040.2-2006, wherein the tensile speed is 50mm/min, the width of a sample is 5.0mm, the thickness of the sample is 2.0mm, each group of 5 samples are tested in parallel, and the average value is taken;
(2) impact strength: testing by using an SE-2 type simply supported beam impact strength tester according to the standard regulation of GB/T1043 + 1993, wherein the impact speed is 3.5m/s, the width of a sample is 10mm, the length of the sample is 80mm, the thickness of the sample is 4.0mm, 5 samples are tested in parallel in each group, and the average value is taken;
(3) combustibility: testing according to UL-94 vertical burning test standard;
(4) flame retardant stability: boiling the polystyrene flame-retardant material in boiling water for 2 hours, drying, and measuring the combustibility of the polystyrene flame-retardant material according to the UL-94 vertical combustion test standard;
(5) mobility: the polystyrene flame retardant material was baked at 150 ℃ for 2 hours, and the weight change rate (%) before and after baking was measured.
The polystyrene flame retardant materials provided in examples 1 to 8 and comparative examples 1 to 6 were tested for tensile strength, elongation at break, impact strength, flammability, flame retardant stability and migration according to the above methods, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the polystyrene flame retardant materials with the reactive phosphorus-containing flame retardant added in examples 1-8 have significantly excellent combustibility and flame retardant stability, and the mechanical properties are improved compared with the polystyrene without flame retardant in comparative example 1, the tensile strength can reach 41-49.5 MPa, the elongation at break is 47.9-53%, and the impact strength reaches 8.5KJ/m2The balance between hardness and toughness is better, and the impact strength is high; the reaction type phosphorus-containing flame retardant with vinyl in the example 1 is replaced by the equivalent additive flame retardant (a comparative example 2 and a comparative example 3), the obtained polystyrene flame retardant material has obviously reduced combustibility and mechanical property, the flame retardant stability is poor, and the flame retardant property of the material is obviously reduced after the material is boiled in water; the combustibility of the material can be optimized by increasing the dosage of the additive flame retardant (comparative example 4), but the flame retardant stability of the material is still poor, the flame retardance is reduced after water boiling, and the weight change rate is large after baking, which shows that the additive flame retardant has low flame retardant efficiency and obvious migration and precipitation phenomena compared with the reactive flame retardant with vinyl. If the content of the reactive phosphorus-containing flame retardant having vinyl groups in the polystyrene flame retardant material is out of the range defined in the present invention, the flame retardant performance cannot be effectively realized if the content of the flame retardant is too low (comparative example 5), and the mechanical properties are reduced and resources are wasted if the content of the flame retardant is too high (comparative example 6) by over-plasticizing the material.
In conclusion, the polystyrene flame-retardant material obtained by introducing the reactive phosphorus-containing flame retardant with vinyl into the preparation raw materials and copolymerizing with styrene in the preparation process has excellent flame retardance, and the flame retardance of the material can reach V-0 level; the flame retardant in the polystyrene flame-retardant material provided by the invention participates in free radical polymerization and stably exists in the material in a molecular chain fragment form, the flame-retardant property of the material is stable, the phenomena of micromolecule precipitation, water solubility or hydrolysis are avoided, the flame-retardant property is not reduced due to the migration and precipitation of the flame retardant caused by operations such as water boiling or baking, and the flame-retardant property of the material after water boiling can still reach V-0 level; more importantly, the reactive flame retardant is completely embedded into the polymer chain segment, the reduction of the mechanical property of the material caused by the compatibility problem of the additive flame retardant can not occur, and the introduction of the reactive phosphorus-containing flame retardant with vinyl has a certain reinforcing and toughening effect on the polystyrene flame retardant material, so that the polystyrene flame retardant material provided by the invention has good mechanical property.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention is implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The polystyrene flame-retardant material is characterized in that the preparation raw materials of the polystyrene flame-retardant material comprise styrene, a reactive phosphorus-containing flame retardant, toughened rubber and an initiator;
the reactive phosphorus-containing flame retardant has a structure shown in a formula I or a formula II:
wherein L is1、L2Each independently selected from a group containing a terminal vinyl group;
Z1、Z2each independently selected from phosphorus-containing groups;
M1selected from linear alkylene, branched alkylene or arylene;
M2selected from any organic group that satisfies a chemical environment;
Y1、Y2each independently selected from an inert group, -OH, a sulfur atom, an oxygen atom, or-H;
X1selected from any organylene group that satisfies a chemical environment;
X2an aliphatic group containing a carbon-carbon double bond selected from C2-C30;
a. b, c, d, f, g and h are respectively and independently selected from integers of 0-5, a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and meanwhile, b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5;
e is an integer of 0 to 100.
2. The polystyrene flame-retardant material according to claim 1, wherein the polystyrene flame-retardant material is prepared from the following raw materials:
3. the polystyrene flame retardant material of claim 1 or 2, wherein L is1、L2Each independently selected from
Wherein j is an integer of 0 to 20, R10Is C1-C10 alkyl, # represents the access position of the group;
preferably, Z is1、Z2Each independently selected from
One of (1), R1Any one selected from saturated or unsaturated alkyl, aryl or heteroaryl, more preferably methyl, ethyl or phenyl;
preferably, said M1Selected from C, N,
O、-O-RT-, C1-C30 straight chain or branched chain alkylene, C6-C30 arylene or C5-C7 heteroarylene, and more preferably
-O-RT-, C1-C5 linear alkylene, C3-C5 branched alkylene, phenyl or naphthyl, more preferably C1-C3 linear alkylene, C3 branched alkylene, phenyl or naphthyl, wherein R isTOne selected from C1-C10 straight chain or branched chain alkyl and C6-C30 aryl;
preferably, said M2Selected from C, N,
O、-O-RT-, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R isTSelected from one of C1-C10 straight chain or branched chain alkyl and C6-C30 aryl, R2-R9Each independently selected from one of C1-C10 straight chain or branched chain alkylene, L2、Y2、Z2Is connected to R2-R9N, m, i, k are each independently selected from integers of 0 to 100;
preferably, said R is2-R9Each independently selected from one of C1-C6 straight chain or branched chain alkylene;
preferably, n, m, i and k are respectively and independently selected from integers of 0-30;
preferably, said Y is1、Y2Each independently selected from-H, -OH, or ═ O;
preferably, said X1One selected from N, S, substituted or unsubstituted C1 to C30 linear or branched alkylene groups, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C5 to C7 heteroarylene groups, substituted or unsubstituted C1 to C30 alkyleneamino groups, substituted or unsubstituted C1 to C30 alkyleneacyl groups, substituted or unsubstituted C1 to C30 alkyleneester groups, substituted or unsubstituted C6 to C30 arylamino groups, substituted or unsubstituted C6 to C30 aryloyl groups or C6 to C30 arylester groups, further preferably substituted or unsubstituted C1 to C5 linear or branched alkylene groups, substituted or unsubstituted C1 to C5 alkyleneamino groups, substituted or unsubstituted C1 to C5 alkyleneacyl groups, and substituted or unsubstituted C1 to C5 alkyleneester groups, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", R ″VEach independently selected from substituted or unsubstituted C1-C10 straight or branched chain alkylene;
preferably, said X2Is composed of
Wherein R isq、RsEach independently selected from a single bond or a C1-C10 alkylene.
4. The flame retardant polystyrene material as claimed in any one of claims 1 to 3, wherein the reactive phosphorus-containing flame retardant preferably has a structure represented by formula III, formula IV, formula V, formula VI, formula VII or formula VIII:
wherein L is1、L2Each independently selected from
Wherein j is an integer of 0 to 3, R10Is C1-C3 alkyl, # represents the access position of the group;
M1is selected from
-O-RTOne of C1-C3 straight chain alkylene, C3 branched chain alkylene, naphthyl or phenyl;
M2selected from C, N,
O、-O-RT-, C1-C6 straight chain or branched chain alkyl,
Wherein R isTIs one of C1-C6 straight chain or branched chain alkyl, phenyl or biphenyl, R2-R9Each independently selected from C1-C6 straight chain or branched chain alkylene, n, m, i and k are each independently selected from integers of 0-30, L2、Y2、Z2Is connected to R2-R9Any connectable location of (a);
R1is methyl or ethyl;
R、R'、R”、RV、RPeach independently selected from substituted or unsubstituted C1-C10 straight or branched chain alkylene;
Rq、Rseach independently selected from a single bond or one of C1-C3 alkylene;
Y1、Y2each independently selected from-H, -OH or ═ O;
a. b, g and h are respectively and independently selected from 0, 1 or 2, a + b is not less than 2, f and g are not 0 at the same time, and g and h are not 0 at the same time;
e is an integer of 0-20, f is 0 or 1;
preferably, the reactive phosphorus-containing flame retardant is further preferably any one of or a combination of at least two of the compounds having the following structures:
wherein R isPOne kind selected from substituted or unsubstituted C1-C8 straight chain or branched chain alkylene, R1Is methyl or ethyl, and e is an integer of 0 to 5.
5. The polystyrene flame retardant material according to any one of claims 1 to 4, wherein the toughened rubber is cis-1, 4-polybutadiene rubber and/or styrene-butadiene rubber, preferably cis-1, 4-polybutadiene rubber;
preferably, the cis-1, 4-polybutadiene rubber includes a low cis-1, 4-polybutadiene rubber and a high cis-1, 4-polybutadiene rubber;
preferably, the initiator is a peroxide initiator;
preferably, the peroxide initiator is selected from one of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide or tert-butyl peroxybenzoate.
6. The polystyrene flame-retardant material according to any one of claims 1 to 5, wherein the polystyrene flame-retardant material is prepared from raw materials which further comprise an organic solvent;
preferably, the organic solvent is ethylbenzene;
preferably, the addition amount of the ethylbenzene is 18 to 23% by mass of the styrene, and more preferably 20%.
7. A preparation method of the polystyrene flame retardant material as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
mixing styrene, a reactive phosphorus-containing flame retardant, a toughening rubber and an initiator, and carrying out bulk graft polymerization to obtain the polystyrene flame retardant material.
8. The preparation method according to claim 7, wherein the reaction temperature of the bulk graft polymerization is 80 to 230 ℃;
preferably, the reaction time of the bulk graft polymerization is 7-20 h;
preferably, the bulk graft polymerization is carried out under stirring conditions;
preferably, the bulk graft polymerization is carried out in a protective atmosphere;
preferably, the protective atmosphere is nitrogen or argon;
preferably, the preparation method also comprises the post-treatment of the product;
preferably, the post-treatment is performed by means of a devolatilization device.
9. The method according to claim 7 or 8, comprising in particular the steps of:
under the protection of nitrogen, mixing styrene, a reactive phosphorus-containing flame retardant, toughened rubber, an initiator and an organic solvent, stirring and reacting for 7-20 h at the temperature of 80-230 ℃, and stopping reaction; and removing residual styrene and organic solvent by using a devolatilization device to obtain the polystyrene flame-retardant material.
10. Use of the flame retardant polystyrene material as claimed in any one of claims 1 to 6 in the housing, lining and automobile parts of electronic and electric appliances.
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