CN112480412A - Acetoacetyl functionalized phosphorus-containing resin flame retardant and preparation method thereof - Google Patents
Acetoacetyl functionalized phosphorus-containing resin flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN112480412A CN112480412A CN202011196951.2A CN202011196951A CN112480412A CN 112480412 A CN112480412 A CN 112480412A CN 202011196951 A CN202011196951 A CN 202011196951A CN 112480412 A CN112480412 A CN 112480412A
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- acetoacetyl
- flame retardant
- compound
- functionalized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
-
- 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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65748—Esters of oxyacids of phosphorus the cyclic phosphorus atom belonging to more than one ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses an acetoacetyl functionalized phosphorus-containing resin flame retardant, which is a resin simultaneously having an acetoacetyl functional group and a phosphorus-containing oxy group. The obtaining steps are as follows: reacting a phosphorus-containing oxy compound and a compound containing at least one acetoacetyl functional group to obtain an acetoacetyl-functionalized phosphorus-containing resin flame retardant. The flame-retardant polymer composition containing the flame retardant has high carbon forming rate, high oxygen index and good flame-retardant effect.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and relates to an acetoacetyl functionalized phosphorus-containing resin flame retardant and a preparation method thereof.
Background
The polymer material has the excellent characteristics of light weight, good chemical stability, easy processing and the like, and has become an important matrix material in the fields of aerospace, transportation, electricians and electronics, building materials and the like. However, most of high polymer materials belong to flammable materials, so that the high polymer materials provide convenience and increase great potential safety hazards. Fire is one of the main disasters threatening public safety, and causes a great amount of casualties and huge economic losses every year. Only in 2017, 1-10 months, 21.9 thousands of fires are reported all over the country, 1065 people and 679 people are killed, and 26.2 million yuan of direct property loss is verified. In 2001, the 'fire-fighting Law' was issued and implemented in China, and the public safety required for fire prevention and flame retardance is a foundation stone for national safety and social stability on the legal level.
The most effective flame retardant coating pastes currently used are still antimony bromide based systems. The bromine antimony type flame retardant system has excellent performance in gas phase flame retardant and high performance-price ratio, and is popular. Antimony, such as the most commonly used antimony oxide, is added into the brominated flame retardant to realize the synergistic effect of the antimony bromide, so that the flame retardant efficiency of the flame retardant system can be greatly improved, and the using amount of the flame retardant is reduced. Although halogen-based flame retardants have many excellent properties, high polymers containing the flame retardants release a large amount of smoke and toxic and corrosive gases (hydrogen halide gases) during combustion, and partially undergo thermal decomposition to form carcinogens of polyhalogenated dibenzodioxanes and polyhalogenated dibenzofurans. Various bromine-containing organic compounds are bioaccumulative, can affect the nervous system, the immune system and the reproductive system of organisms, and are global environmental pollutants.
The intumescent phosphorus-containing composite flame retardant system replaces bromine antimony type flame retardant and is a novel composite flame retardant which is widely concerned in the field of national flame retardance in recent years. The intumescent composite flame retardant adopts an acid source, a carbon source and a gas source to realize synergistic flame retardance, and is a classic synergistic combination in the field of flame retardance. The intumescent flame retardant system can realize high-efficiency char formation flame retardance through condensed phase flame retardance. A compact porous foam carbon layer is formed on the surface of the fabric, so that the further degradation of the inner high polymer and the release of combustible materials to the surface can be prevented, the transmission of a heat source to the high polymer can be prevented, and an oxygen source is isolated, so that the spread and the propagation of flame can be prevented. Although the intumescent flame retardant has the advantages of no halogen, low smoke, low toxicity, molten drop prevention and no corrosive gas, the intumescent flame retardant is inferior to a bromine-antimony flame retardant system in the aspects of flame retardant efficiency, heat resistance, water washing resistance and the like.
It is well known that polymers may be provided with certain additional functionalities, such as reactivity or compatibility with other components, by introducing certain functional groups into the polymer molecule. Acetoacetyl functionality is an attractive functional group for modifying or functionalizing polymers because the active methylene group between two carbonyl moieties in the functional group can react with various functional groups such as isocyanate groups, amine groups, unsaturated double bonds, aldehyde groups, and the like. It has been contemplated that acetoacetyl-functionalized phosphorus-containing resin flame retardants, when incorporated into compositions containing other polymeric components and/or curing agents with functional groups (such as isocyanates, amines, melamines, unsaturated double bonds, and aldehydes), can react with the other polymeric components or curing agents to become at least part of the crosslinked network, thereby serving to anchor the phosphorus-containing flame retardant within the polymer network, preventing migration and leaching of the flame retardant, and thus providing advantageous flame retardant properties. Meanwhile, the hyperbranched polymer has a dendritic, hyperbranched and 3D structure, the spatial structure is spherical, and the surface of the hyperbranched polymer can be constructed with a large number of different active functional groups. The special structure of the hyperbranched polymer endows the hyperbranched polymer with special properties, and the hyperbranched polymer has great application value in various fields such as coating, flame retardant, nanotechnology, biological materials, engineering plastics and the like.
At present, a halogen-free flame retardant system which integrates or partially integrates the advantages of a bromine-antimony flame retardant system and an intumescent phosphorus-containing composite flame retardant system and overcomes the disadvantages of the bromine-antimony flame retardant system and the intumescent phosphorus-containing composite flame retardant system is urgently needed in the market.
Disclosure of Invention
The invention aims to provide an acetoacetyl functionalized phosphorus-containing resin flame retardant and a preparation method thereof.
The invention provides an acetoacetyl functionalized phosphorus-containing resin flame retardant, which adopts the technical scheme that:
the flame retardant is a resin which simultaneously has an acetoacetyl functional group and a phosphorus-containing oxy group.
The flame retardant is obtained by the following steps: reacting a phosphorus-containing oxy compound and a compound containing at least one acetoacetyl functional group to obtain an acetoacetyl-functionalized phosphorus-containing resin flame retardant.
The phosphorus-oxygen-containing compound is selected from one or a combination of more than two of pentaerythritol phosphate, cyclooctyl (3-hydroxypropyl) phosphine oxide, 4-hydroxyphenyl diphenyl phosphine oxide, bis (4-hydroxyphenyl) phenyl phosphine oxide, tris (3-hydroxypropyl) phosphine oxide, 4-hydroxymethyl phosphine oxide, phenol or alcohol derivatives of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), phosphorus oxychloride, dimethyl chlorophosphate, diethyl chlorophosphate, dibutyl chlorophosphate, diisooctyl chlorophosphate, diphenyl chlorophosphate and dibutoxyethyl chlorophosphate; the compound containing the acetoacetyl functional group is selected from one or the combination of more than two of allyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, diketene and derivatives of the above substances.
The flame retardant has a hyperbranched molecular structure, and the structural formula is as follows:
in the formula: m represents a hyperbranched polymer skeleton, R is a phosphorus-containing oxy group, Q is an acetoacetyl functional group, n and M are natural numbers respectively, and n + M is more than or equal to 2 and less than or equal to 48.
M in the structural formula is hyperbranched organic silicon resin (organic silicon resin is also called silicon-based resin).
The phosphorus-containing resin flame retardant contains at least 1 phosphorus-containing oxy group and at least 1 acetoacetyl functional group on average per polymer chain, or contains at least 4 phosphorus-containing oxy groups and at least 4 acetoacetyl functional groups on average per polymer chain.
The acetoacetyl functionalized phosphorus-containing resin flame retardant has the number average molecular weight of 250g/mol to 20000 g/mol; the number average molecular weight is preferably 500-15000 g/mol, more preferably 1000-10000g/mol, and still more preferably 2000-10000 g/mol.
The phosphorus-containing resin flame retardant has a branched silicon atom-containing molecular skeleton and phosphorus-containing oxy groups and acetoacetyl-containing functional groups chemically bonded to silicon atoms of the molecular skeleton, the acetoacetyl-functionalized phosphorus-containing resin flame retardant being obtained by: (1) reacting a silane compound having three or more condensable functional groups with at least one hydroxyl-containing compound to form a branched silicon-based resin, (2) introducing a phosphorus-containing oxy group and an acetoacetyl-containing functional group onto the silicon-based resin to obtain an acetoacetyl-functionalized phosphorus-containing resin flame retardant.
One of the preparation methods of the phosphorus-containing resin flame retardant comprises the following steps:
(1) reacting a silane compound with more than three condensable functional groups with a hydroxyl-containing compound at the temperature of 110-180 ℃, and obtaining a branched silicon-based resin taking the condensable functional groups of the silane compound as end groups after the reaction is finished; wherein the molar ratio of the hydroxyl group-containing compound to the condensable functional group of the silane compound is 1: 1.2 to 1: 4.0;
(2) adding a phosphorus-oxygen-containing compound and a compound containing an acetoacetyl functional group into the silicon-based resin prepared in the step (1) in any proportion, reacting at the temperature of 80-180 ℃, and preparing an acetoacetyl-functionalized phosphorus-containing resin flame retardant after the reaction is finished; the phosphorus-oxygen-containing compound is selected from one or the combination of more than two of pentaerythritol phosphate, cyclooctyl (3-hydroxypropyl) phosphine oxide and 4-hydroxyphenyl diphenyl phosphine oxide; the compound containing the acetoacetyl functional group is selected from one or the combination of more than two of allyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, diketene and derivatives of the above substances; wherein the molar ratio of the compound containing the phosphorus-oxygen radical and the compound containing the acetoacetyl functional group to the end group of the condensation functional group on the surface of the silicon-based resin is 0.1: 1 to 1:1.
the second preparation method of the phosphorus-containing resin flame retardant comprises the following steps:
(1) reacting a silane compound with more than three condensation functional groups with a hydroxyl-containing compound at the temperature of 110-180 ℃ to obtain a branched silicon-based resin with hydroxyl as a terminal group after the reaction is finished; the molar ratio of the condensable functional group of the silane compound to the hydroxyl group of the hydroxyl group-containing compound is 1: 1.2 to 1: 4;
(2) adding a phosphorus-oxygen-containing compound and a compound containing an acetoacetyl functional group into the silicon-based resin prepared in the step (1) in any proportion, reacting at the temperature of 80-180 ℃, and preparing the acetoacetyl-functionalized phosphorus-containing resin flame retardant after the reaction is finished; the phosphorus-oxygen-containing compound is one or the combination of more than two of phosphorus oxychloride, dimethyl chlorophosphate, diethyl chlorophosphate, dibutyl chlorophosphate, diisooctyl chlorophosphate, diphenyl chlorophosphate and dibutoxyethyl chlorophosphate; the compound containing the acetoacetyl functional group is selected from one or the combination of more than two of allyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, diketene and derivatives of the above substances; wherein the molar ratio of the compound containing the phosphorus-oxygen radical and the compound containing the acetoacetyl functional group to the hydroxyl functional group terminal group on the surface of the silicon-based resin is 0.1: 1 to 1:1.
the silane compound having three or more condensable functional groups is selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, hexadecyltrimethoxysilane, octyltriethoxysilane, mercaptopropyltrimethoxysilane, N-aminoacyl-3-aminopropyltriethoxysilane, vinyltriethoxysilane, glycidyloxypropyltrimethoxysilane, methyltriacetoxysilane, methyltributanonoximinosilane, methyltriisopropyloxysilane, alpha-monomethyl, one or more of omega-trimethoxy polydimethylsiloxane, alpha-monomethyl, omega-triethoxy polydimethylsiloxane and alpha-monomethyl, omega-tripropoxy polydimethylsiloxane.
The hydroxyl-containing compound is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 2-methylpropanediol, 2-methyl-2-hydroxymethylpropanediol, neopentylglycol, glycerol, 2, 4-trimethyl-1, 3-pentanediol, 2-dimethyl-3-hydroxypropionic acid 2, 2-dimethyl-3-hydroxypropyl ester, bisphenol A, bisphenol F, bisphenol S, 1, 3-butylethylpropanediol, 2-methyl-1, 3-propanediol, cyclohexanedimethanol, 1, 4-benzyldimethanol, 1, 4-benzyldiethanol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol, 1, 4-cyclohexane diethanol, hydroquinone, phenylene dimethanol, resorcinol, naphthalenediol, anthracene-1, 10-diol and tris (2-hydroxyethyl) cyanurate.
The invention can be used for preparing a flame-retardant polymer composition, and the flame-retardant polymer composition comprises an acetoacetyl functionalized phosphorus-containing resin flame retardant and a high molecular polymer; the flame-retardant polymer composition may contain a flame retardant, and may further contain an additive; the high molecular polymer comprises one or the combination of more than two of alkyd resin, epoxy resin, phenolic resin, polyester resin, acrylic resin, polyurethane resin, PVC resin, nylon resin, ABS resin, PC resin and polyvinyl alcohol resin.
The flame-retardant polymer composition has high carbon forming rate, high oxygen index and good flame-retardant effect. The hyperbranched acetoacetyl functionalized phosphorus-containing resin flame retardant has a unique 3D spherical macromolecular structure, can play a role in lubricating in the processing of flame-retardant macromolecules and reduces the processing temperature. Meanwhile, due to the existence of the acetoacetyl functional group, the hyperbranched acetoacetyl functionalized phosphorus-containing resin flame retardant can perform crosslinking reaction with crosslinkable groups of a polymer matrix, such as aldehyde group, isocyanate, amino group and the like, so that the migration of the flame retardant is prevented, the strength of the polymer matrix is further enhanced, and the flame-retardant high-molecular polymer with better comprehensive performance is obtained.
Where the method of preparation of the present invention is described as including or comprising particular process steps, it is contemplated that optional process steps not contemplated by the present invention are not excluded from the method, and that the method may consist or consist of the process steps involved.
Drawings
FIG. 1 is an FTIR spectrum of the reaction starting materials and reaction products of example 1;
FIG. 2 is FTIR spectra of reaction raw materials and reaction products of step (1) of example 3;
FIG. 3 is FTIR spectra of the reaction raw materials and reaction products of step (2) of example 3.
Detailed Description
The following examples are provided to illustrate the applicability of the present invention, and should not be construed as limiting the scope of the invention to the specific examples set forth below. Further, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.
Example 1
In one embodiment of the present invention, while not wishing to be bound by any theory, the inventors believe that the t-butyl acetoacetate and pentaerythritol phosphate in the examples follow the reaction represented by the following schematic formula A.
As the raw material for introducing the phosphorus-containing oxy group, various kinds of hydroxyl-containing phosphate esters can be used, preferably pentaerythritol phosphate, cyclooctyl (3-hydroxypropyl) phosphine oxide, 4-hydroxyphenyldiphenylphosphine oxide, tris (3-hydroxypropyl) phosphine oxide, 4-hydroxymethylphosphine oxide. As the raw material for introducing an acetoacetyl group, various types of derivatives containing an acetoacetyl group may be used, and preferably a group consisting of allyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, diketene, derivatives thereof, and combinations thereof. In one embodiment, pentaerythritol phosphate and t-butyl acetoacetate are used for the reaction. The reaction is carried out under the conditions of heating temperature of 110-180 ℃ without any catalyst and any solvent. In order to increase the reaction rate, a catalyst and a solvent may also be used in appropriate amounts.
The reaction mixture is maintained at an elevated temperature for a sufficient period of time until the release of t-butanol ceases, thereby forming an acetoacetyl-functionalized phosphorus-containing resin flame retardant of the following schematic formula A;
the specific implementation mode is as follows: 158.20g of tert-butyl acetoacetate were weighed into a constant pressure burette and placed in a four-necked flask containing 180.10g of pentaerythritol phosphate and 100ml of ethyl 3-ethoxypropionate (EEP) with thermometer, overhead stirrer, gas inlet and distillation apparatus. The reaction mixture was then heated to 120 ℃ and maintained at that temperature. The tert-butyl acetoacetate was added to the three-necked flask at a rate of one second and one drop, and the addition was controlled to be completed within 1 hour. The reaction was carried out under the protection of a stream of anhydrous nitrogen introduced through the gas inlet of the reactor until distillate distilled from the reaction mixture. Then, heating was continued and the temperature of the reaction mixture was raised to 140 ℃ until the tert-butanol was distilled off completely. Thus, a resin flame retardant containing both an acetoacetyl functional group and a phosphorus-oxygen-containing group (phosphorus-containing resin flame retardant) was obtained. The results of infrared spectrum FTIR are shown in fig. 1.
Example 2
The invention relates to an acetoacetyl functionalized phosphorus-containing organic silicon resin flame retardant with a hyperbranched macromolecular structure, which comprises a branched silicon atom-containing molecular skeleton and phosphorus-containing oxy groups and acetoacetyl functional groups chemically bonded to silicon atoms of the molecular skeleton, wherein the acetoacetyl functionalized phosphorus-containing organic silicon resin flame retardant with the hyperbranched macromolecular structure is obtained by the following steps: (1) performing a condensation reaction of a silane compound having three or more condensable functional groups with an excess of at least one polyol to form a silicon-based resin having hydroxyl groups as terminal groups, and (2) introducing a phosphorus-containing oxy group and an acetoacetyl-containing functional group on the hydroxyl-terminated silicon-based resin to obtain an acetoacetyl-functionalized phosphorus-containing silicone resin flame retardant having a hyperbranched macromolecular structure (phosphorus-containing resin flame retardant). The step (1) is carried out at a reaction temperature of 110-180 ℃; the step (2) is respectively carried out at the reaction temperature of 80-180 ℃.
Suitable conditions for the reaction carried out in steps (1) and (2) of the present invention depend on various factors including the type of silane compound, polyol or phosphorus-containing oxy compound used, the presence or absence of a catalyst, the type of catalyst, the presence or absence of a solvent, and the like, which can be empirically determined by those skilled in the art.
In one embodiment of the present invention, step (1) tetraethoxysilane is used as the silane compound having three or more condensable functional groups, and neopentyl glycol is used as the polyol. Controlling the mole ratio of the ethoxy groups of the tetraethoxysilane to the hydroxyl groups of the neopentyl glycol to be 1: 1.2 to 1: 4, preferably in the range of 1:1.4 to 1: 2.5, more preferably in the range of 1:1.5 to 1: 2.0, into the reactor. Stirring at the high temperature of 120-180 ℃ in the absence of a catalyst and a solvent, and reacting for 5-20 hours; to prepare the silicon-based resin taking hydroxyl as a terminal group. In order to increase the reaction rate, a catalyst and an organic solvent may also be used in appropriate amounts.
While not wishing to be bound by any theory, the inventors believe that tetraethoxysilane and neopentyl glycol in the examples follow a reaction represented by the following schematic formula B:
in the step (2), an acetoacetyl functional group and a phosphorus-oxygen-containing group are simultaneously introduced into the silicon-based resin which takes the hydroxyl as the terminal group and is obtained in the step (1), so that the acetoacetyl functionalized phosphorus-containing resin flame retardant with the hyperbranched macromolecular structure is formed. As the raw material for introducing the phosphorus-containing oxy group, various types of chlorinated phosphoric esters can be used, and phosphorus oxychloride, dimethyl chlorophosphate, diethyl chlorophosphate, dibutyl chlorophosphate, diisooctyl chlorophosphate, and diphenyl chlorophosphate are preferable. In one embodiment, the above-described hydroxyl-terminated silicon-based resins are preferably functionalized with di-n-butyl chlorophosphate and t-butyl acetoacetate. The reaction is carried out by reduced pressure distillation under the condition of proper amount of solvent and catalyst. Preferably, the above reaction is carried out without any catalyst, without any solvent, under heating temperature conditions of 80 to 180 ℃. The reaction mixture is maintained at elevated temperature and distilled under reduced pressure for a sufficient period of time until di-n-butyl chlorophosphate and t-butyl acetoacetate are consumed, thereby forming the acetoacetyl-functionalized phosphorus-containing silicone resin flame retardant having a hyperbranched macromolecular structure, as shown in schematic formula C below;
in the reaction formulas B and C, n represents an integer of 1 to 10.
The specific embodiment is as follows: 208.33g of tetraethoxysilane and 156.22g of neopentyl glycol were added at room temperature to a four-necked flask equipped with a thermometer, overhead stirrer, gas inlet and distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 115 ℃ and maintained at that temperature until distillate distilled from the reaction mixture. 97.10g of trimethylolpropane are then added, heating is continued and the temperature of the reaction mixture is raised stepwise to 180 ℃ until the ethanol has distilled off completely. In this way, hyperbranched polysiloxanes containing hydroxyl groups are obtained.
After the reaction mixture was charged with the appropriate solvent and catalyst and the temperature was reduced below 80 ℃, 202.20g of di-n-butyl chlorophosphate were added. The temperature of the reaction mixture was then controlled at 92-100 ℃ for reflux and maintained at that temperature until HCl evolution ceased. Adding 110.10g of tert-butyl acetoacetate to the reaction mixture, heating the mixture and slowly raising the temperature of the reaction mixture to 140 ℃ until the tert-butyl alcohol is completely distilled off; obtaining the acetoacetyl functionalized phosphorus-containing resin flame retardant with a hyperbranched macromolecular structure.
Example 3
The specific embodiment is as follows: step (1) 208.33g (1.00mol) of tetraethoxysilane and 374.94g (3.60mol) of neopentyl glycol were added at room temperature to a four-necked flask equipped with a thermometer, overhead stirrer, gas inlet and distillation apparatus. The reaction was carried out under the protection of an anhydrous nitrogen stream introduced through the gas inlet of the reactor. The reaction mixture was then heated to 115 ℃ and maintained at that temperature until distillate distilled from the reaction mixture. Heating was continued and the temperature of the reaction mixture was gradually raised to 180 ℃ until the ethanol was distilled off completely. In this way, a hyperbranched polysiloxane containing hydroxyl groups (hyperbranched polysiloxane) was obtained. The results of IR spectroscopy are shown in FIG. 2.
Step (2) 158.19g (1.00mol) of t-butyl acetoacetate were added dropwise to the reaction mixture, heating was continued and the temperature of the reaction mixture was slowly raised to 140 ℃ until the t-butanol was distilled off completely. At this time, the reaction temperature was lowered to 93 ℃ to 100 ℃, and a mixed solution of 402.95g (1.50mol) of diphenyl chlorophosphate and 250ml of Dimethylacetamide (DMAC) was further added dropwise to the reaction mixture. And reacting for 7.5-8.0 h after the dropwise adding is finished, and testing the pH value in the three-neck flask every ten minutes until the pH value is no longer acidic, so as to obtain the resin flame retardant (phosphorus-containing resin flame retardant) which has a hyperbranched macromolecular structure and contains the acetoacetyl functional group and the phosphorus-oxygen containing group. The results of IR spectroscopy are shown in FIG. 3.
Example 4
In another aspect of the present invention, there is provided a flame retardant polymeric composition comprising an acetoacetyl-functionalized phosphorus-containing resin flame retardant of the present invention, optionally a polymeric compound, a flame retardant, and additional additives. Wherein the high molecular polymer includes, but is not limited to, alkyd resin, epoxy resin, phenolic resin, polyester resin, acrylic resin, polyurethane resin, PVC resin, nylon resin, ABS resin, PC resin, polyvinyl alcohol resin, or a combination thereof.
The resin flame retardant (phosphorus-containing resin flame retardant) containing the acetoacetyl functional group and the phosphorus-oxygen containing group, which has the hyperbranched macromolecular structure obtained in example 3, was added to the following high molecular polymers at a mass fraction of 20% respectively, and the mixture was uniformly mixed, and then the mixture was tableted to prepare a sample, and a thermal weight loss test was performed, and the test results are shown in table 1 below.
The resin flame retardant (phosphorus-containing resin flame retardant) which has the hyperbranched macromolecular structure and contains the acetoacetyl functional group and the phosphorus-oxygen group in the embodiment 3 is respectively added into the polymer PVA and the polymer PS according to the weight ratio of 20 percent, so that the carbon forming rate of the PVA can be increased from 17.5 percent to 23.5 percent and is higher than the carbon forming rate of 20.4 percent of the traditional flame retardant RDP/PVA compound under the same proportion; the carbon forming rate of the PS can be improved from 1.3% to 6.6%, and is obviously higher than the carbon forming rate of 2.2% of the traditional flame retardant RDP/PS compound under the same proportion.
The resin flame retardant disclosed by the invention has excellent performance of catalyzing polymers to form carbon. Example 4 was repeated with similar results using the hyperbranched phosphorus (oxy) group-containing functionalized silicon-based resin flame retardant of example 2.
Table 1.
| Item(s) | Components | 700oC carbon formation Rate (w%) |
| 1 | PVA (polyvinyl alcohol) | 17.5 |
| 2 | PVA +20% acetoacetyl functionalized phosphorus-containing resin flame retardant | 23.5 |
| 3 | PVA +20% RDP (m-phenylene tetraphenyl diphosphate) | 20.4 |
| 4 | PS (polystyrene) | 1.3 |
| 5 | PS +20% acetoacetyl functionalized phosphorus-containing resin flame retardant | 6.6 |
| 6 | PS +20% RDP (m-phenylene tetraphenyl diphosphate) | 2.2 |
Example 5
The acetoacetyl functionalized phosphorus-containing resin flame retardant prepared in example 3, 20% of APP (ammonium polyphosphate, polymerization degree greater than 1000) and 10% of carbon forming agent (hyperbranched triazine carbon forming agent), which are in a mass fraction ratio of 10%, are added into PVA to be uniformly mixed, and then the mixture is tableted to prepare a sample, and a UL-94 flame retardant performance test is carried out to achieve flame retardant V0 level. The test results are shown in Table 2.
Table 2.
| Item(s) | Components | UL-94 flame retardant rating |
| 1 | PVA (polyvinyl alcohol) | - |
| 2 | PVA +10% acetoacetyl functionalized phosphorus-containing resin flame retardant +20% APP +10% carbon forming agent | V0 |
Example 6
The acetoacetyl functionalized phosphorus-containing resin flame retardant prepared in example 3, 20% of APP (ammonium polyphosphate, polymerization degree greater than 1000) and 10% of carbon forming agent (hyperbranched triazine carbon forming agent), in a mass fraction ratio, were added to PS and mixed uniformly, and the mixture was tableted to prepare a sample, and subjected to an oxygen index (LOI) flame retardant performance test. . The test results are shown in Table 3.
Table 3.
| Item(s) | Components | Oxygen Index (LOI) |
| 1 | PS (polystyrene) | 18.5 |
| 2 | 60% PS +10% acetoacetyl functionalized phosphorus-containing resin flame retardant +20% APP +10% carbon former | 21.2 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification of the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (12)
1. An acetoacetyl-functionalized phosphorus-containing resin flame retardant characterized by: the flame retardant is a resin which simultaneously has an acetoacetyl functional group and a phosphorus-containing oxy group.
2. An acetoacetyl-functionalized phosphorous-containing resin flame retardant as in claim 1, which is obtained by: reacting a phosphorus-containing oxy compound and a compound containing at least one acetoacetyl functional group to obtain an acetoacetyl-functionalized phosphorus-containing resin flame retardant.
3. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 2 wherein: the phosphorus-oxygen-containing compound is selected from one or a combination of more than two of pentaerythritol phosphate, cyclooctyl (3-hydroxypropyl) phosphine oxide, 4-hydroxyphenyl diphenyl phosphine oxide, bis (4-hydroxyphenyl) phenyl phosphine oxide, tris (3-hydroxypropyl) phosphine oxide, 4-hydroxymethyl phosphine oxide, phenol or alcohol derivatives of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), phosphorus oxychloride, dimethyl chlorophosphate, diethyl chlorophosphate, dibutyl chlorophosphate, diisooctyl chlorophosphate, diphenyl chlorophosphate and dibutoxyethyl chlorophosphate; the compound containing the acetoacetyl functional group is selected from one or the combination of more than two of allyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, diketene and derivatives of the above substances.
4. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 1, 2 or 3 wherein: the flame retardant has a hyperbranched molecular structure, and the structural formula is as follows:
in the formula: m represents a hyperbranched polymer skeleton, R is a phosphorus-containing oxy group, Q is an acetoacetyl functional group, n and M are natural numbers respectively, and n + M is more than or equal to 2 and less than or equal to 48.
5. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 4 wherein: m in the structural formula is hyperbranched organic silicon resin.
6. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 1, 2 or 3 wherein: the phosphorus-containing resin flame retardant contains at least 1 phosphorus-containing oxy group and at least 1 acetoacetyl functional group on average or contains at least 4 phosphorus-containing oxy groups and at least 4 acetoacetyl functional groups on average on each macromolecular chain.
7. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 1, 2 or 3 wherein: the acetoacetyl functionalized phosphorus-containing resin flame retardant has a number average molecular weight of 250g/mol to 20000 g/mol.
8. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 5 wherein: having a branched silicon atom-containing molecular skeleton and a phosphorus-containing oxy group and an acetoacetyl-containing functional group chemically bonded to a silicon atom of the molecular skeleton, the acetoacetyl-functionalized phosphorus-containing resin flame retardant being obtained by: (1) reacting a silane compound having three or more condensable functional groups with at least one hydroxyl-containing compound to form a branched silicon-based resin, (2) introducing a phosphorus-containing oxy group and an acetoacetyl-containing functional group onto the silicon-based resin to obtain an acetoacetyl-functionalized phosphorus-containing resin flame retardant.
9. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 8 wherein: the preparation method of the phosphorus-containing resin flame retardant comprises the following steps:
(1) reacting a silane compound with more than three condensable functional groups with a hydroxyl-containing compound at the temperature of 110-180 ℃, and obtaining a branched silicon-based resin taking the condensable functional groups of the silane compound as end groups after the reaction is finished; wherein the molar ratio of the hydroxyl group-containing compound to the condensable functional group of the silane compound is 1: 1.2 to 1: 4.0;
(2) adding a phosphorus-oxygen-containing compound and a compound containing an acetoacetyl functional group into the silicon-based resin prepared in the step (1) in any proportion, reacting at the temperature of 80-180 ℃, and preparing an acetoacetyl-functionalized phosphorus-containing resin flame retardant after the reaction is finished; the phosphorus-oxygen-containing compound is selected from one or the combination of more than two of pentaerythritol phosphate, cyclooctyl (3-hydroxypropyl) phosphine oxide and 4-hydroxyphenyl diphenyl phosphine oxide; the compound containing the acetoacetyl functional group is selected from one or the combination of more than two of allyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, diketene and derivatives of the above substances; wherein the molar ratio of the compound containing the phosphorus-oxygen radical and the compound containing the acetoacetyl functional group to the end group of the condensation functional group on the surface of the silicon-based resin is 0.1: 1 to 1:1.
10. an acetoacetyl-functionalized phosphorus-containing resin flame retardant as in claim 8 wherein: the preparation method of the phosphorus-containing resin flame retardant comprises the following steps:
(1) reacting a silane compound with more than three condensation functional groups with a hydroxyl-containing compound at the temperature of 110-180 ℃ to obtain a branched silicon-based resin with hydroxyl as a terminal group after the reaction is finished; the molar ratio of the condensable functional group of the silane compound to the hydroxyl group of the hydroxyl group-containing compound is 1: 1.2 to 1: 4;
(2) adding a phosphorus-oxygen-containing compound and a compound containing an acetoacetyl functional group into the silicon-based resin prepared in the step (1) in any proportion, reacting at the temperature of 80-180 ℃, and preparing the acetoacetyl-functionalized phosphorus-containing resin flame retardant after the reaction is finished; the phosphorus-oxygen-containing compound is one or the combination of more than two of phosphorus oxychloride, dimethyl chlorophosphate, diethyl chlorophosphate, dibutyl chlorophosphate, diisooctyl chlorophosphate, diphenyl chlorophosphate and dibutoxyethyl chlorophosphate; the compound containing the acetoacetyl functional group is selected from one or the combination of more than two of allyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, diketene and derivatives of the above substances; wherein the molar ratio of the compound containing the phosphorus-oxygen radical and the compound containing the acetoacetyl functional group to the hydroxyl functional group terminal group on the surface of the silicon-based resin is 0.1: 1 to 1:1.
11. an acetoacetyl-functionalized phosphorus-containing resin flame retardant as in any of claims 8-10, wherein: the silane compound having three or more condensable functional groups is selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, hexadecyltrimethoxysilane, octyltriethoxysilane, mercaptopropyltrimethoxysilane, N-aminoacyl-3-aminopropyltriethoxysilane, vinyltriethoxysilane, glycidyloxypropyltrimethoxysilane, methyltriacetoxysilane, methyltributanonoximinosilane, methyltriisopropyloxysilane, alpha-monomethyl, one or more of omega-trimethoxy polydimethylsiloxane, alpha-monomethyl, omega-triethoxy polydimethylsiloxane and alpha-monomethyl, omega-tripropoxy polydimethylsiloxane.
12. An acetoacetyl-functionalized phosphorus-containing resin flame retardant as in any of claims 8-10, wherein: the hydroxyl-containing compound is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 2-methylpropanediol, 2-methyl-2-hydroxymethylpropanediol, neopentylglycol, glycerol, 2, 4-trimethyl-1, 3-pentanediol, 2-dimethyl-3-hydroxypropionic acid 2, 2-dimethyl-3-hydroxypropyl ester, bisphenol A, bisphenol F, bisphenol S, 1, 3-butylethylpropanediol, 2-methyl-1, 3-propanediol, cyclohexanedimethanol, 1, 4-benzyldimethanol, 1, 4-benzyldiethanol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol, 1, 4-cyclohexane diethanol, hydroquinone, phenylene dimethanol, resorcinol, naphthalenediol, anthracene-1, 10-diol and tris (2-hydroxyethyl) cyanurate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011196951.2A CN112480412A (en) | 2020-10-31 | 2020-10-31 | Acetoacetyl functionalized phosphorus-containing resin flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011196951.2A CN112480412A (en) | 2020-10-31 | 2020-10-31 | Acetoacetyl functionalized phosphorus-containing resin flame retardant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112480412A true CN112480412A (en) | 2021-03-12 |
Family
ID=74927944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011196951.2A Pending CN112480412A (en) | 2020-10-31 | 2020-10-31 | Acetoacetyl functionalized phosphorus-containing resin flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112480412A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461963A (en) * | 2021-07-15 | 2021-10-01 | 山东天一化学股份有限公司 | Functionalized hyperbranched phosphorus-containing intumescent flame retardant, preparation method and flame-retardant polymer coating composition |
| CN114702653A (en) * | 2022-06-07 | 2022-07-05 | 欧尚元(天津)有限公司 | Flame-retardant polylactic acid copolymer and preparation method thereof |
| CN116640450A (en) * | 2023-06-15 | 2023-08-25 | 安徽工业大学 | Rubber based on sulfur-containing industrial solid waste and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005078012A2 (en) * | 2004-02-18 | 2005-08-25 | Huntsman Advanced Materials (Switzerland) Gmbh | Fire retardant compositions using siloxanes |
| CN101935399A (en) * | 2010-07-28 | 2011-01-05 | 杭州师范大学 | Method for preparing phosphorus-containing organosilicon flame retardant |
| CN103242533A (en) * | 2012-02-10 | 2013-08-14 | 广东华润涂料有限公司 | Acetoacetyl functionalized silicon-based resin and preparation method thereof |
| CN104011176A (en) * | 2011-10-31 | 2014-08-27 | 路博润高级材料公司 | Non-halogen flame retardant polymers |
-
2020
- 2020-10-31 CN CN202011196951.2A patent/CN112480412A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005078012A2 (en) * | 2004-02-18 | 2005-08-25 | Huntsman Advanced Materials (Switzerland) Gmbh | Fire retardant compositions using siloxanes |
| CN101935399A (en) * | 2010-07-28 | 2011-01-05 | 杭州师范大学 | Method for preparing phosphorus-containing organosilicon flame retardant |
| CN104011176A (en) * | 2011-10-31 | 2014-08-27 | 路博润高级材料公司 | Non-halogen flame retardant polymers |
| CN103242533A (en) * | 2012-02-10 | 2013-08-14 | 广东华润涂料有限公司 | Acetoacetyl functionalized silicon-based resin and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461963A (en) * | 2021-07-15 | 2021-10-01 | 山东天一化学股份有限公司 | Functionalized hyperbranched phosphorus-containing intumescent flame retardant, preparation method and flame-retardant polymer coating composition |
| CN114702653A (en) * | 2022-06-07 | 2022-07-05 | 欧尚元(天津)有限公司 | Flame-retardant polylactic acid copolymer and preparation method thereof |
| CN114702653B (en) * | 2022-06-07 | 2022-08-09 | 欧尚元(天津)有限公司 | Flame-retardant polylactic acid copolymer and preparation method thereof |
| CN116640450A (en) * | 2023-06-15 | 2023-08-25 | 安徽工业大学 | Rubber based on sulfur-containing industrial solid waste and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112480412A (en) | Acetoacetyl functionalized phosphorus-containing resin flame retardant and preparation method thereof | |
| CN112409599B (en) | Hyperbranched silicon-based resin flame retardant containing phosphorus-oxygen functionalized and preparation method thereof | |
| CN112625244B (en) | Hyperbranched phosphorus-containing organic silicon intumescent flame retardant, preparation method and flame-retardant polymer coating composition | |
| CN104403128B (en) | Preparation method containing the biradical structure phosphonium flame retardants of phosphonitrile/DOPO | |
| CN106633066B (en) | A kind of preparation method of organic silicon fibre retardant | |
| CN112250858B (en) | Method for preparing flame-retardant polymer polyol, application and polyurethane foam plastic prepared by using flame-retardant polymer polyol | |
| TWI352114B (en) | ||
| CN106432340B (en) | Phosphorus flame retardant with composite structure and containing multiple DOPO cyclic phosphate and preparation method thereof | |
| CN109912799B (en) | Phosphorus-containing organic silicon flame retardant and preparation and application thereof | |
| CN113461963A (en) | Functionalized hyperbranched phosphorus-containing intumescent flame retardant, preparation method and flame-retardant polymer coating composition | |
| CN114426701B (en) | Preparation of P-N compound synergistic graphene oxide flame retardant and application of P-N compound synergistic graphene oxide flame retardant in epoxy resin | |
| CN113845840B (en) | Epoxy modified organic silicon flame-retardant coating and application thereof | |
| CN114752038A (en) | Halogen-free flame-retardant epoxy resin and preparation method thereof | |
| CN112048157A (en) | Preparation method of flame-retardant epoxy resin composite material | |
| CN111285990B (en) | Preparation of triazine ring-containing triphosphonic acid and derivative compound high-performance reactive polyurethane flame retardant | |
| TW201125873A (en) | Hydroxyphenyl phosphine oxide mixtures and their use as flame retardants for epoxy resins | |
| CN111662421A (en) | Intrinsic flame-retardant cardanol-based phenolic epoxy resin and preparation method thereof | |
| CN112679545A (en) | Melamine-based nitrogen-phosphorus-containing compound, preparation method and application thereof, and flame-retardant epoxy resin composition thereof | |
| CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
| CN112646510A (en) | Preparation of novel flame retardant and application of novel flame retardant in flame-retardant adhesive | |
| CN113402712B (en) | Phosphorus-containing ladder-shaped polysiloxane and preparation method and application thereof | |
| CN113637160B (en) | Triazine structure-containing phosphorus-nitrogen star flame retardant, and preparation method and application thereof | |
| CN113234228B (en) | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof | |
| CN112538245B (en) | Daylighting tile resin and preparation method thereof | |
| EP2352742B1 (en) | Phosphorus-containing silsesquioxane derivatives as flame retardants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210312 |