CN108948424A - A kind of response type phosphonium flame retardant and its preparation method and application - Google Patents
A kind of response type phosphonium flame retardant and its preparation method and application Download PDFInfo
- Publication number
- CN108948424A CN108948424A CN201710361025.8A CN201710361025A CN108948424A CN 108948424 A CN108948424 A CN 108948424A CN 201710361025 A CN201710361025 A CN 201710361025A CN 108948424 A CN108948424 A CN 108948424A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- added dropwise
- reaction
- temperature
- solution
- 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.)
- Granted
Links
Classifications
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- 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
- C08K5/5398—Phosphorus bound to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- 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 present invention provides a kind of response type phosphonium flame retardants, which, which contains unsaturated double-bond, to react with polymer, and phosphate and phosphamide structural unit of the present invention is also introduced on the basis of the unsaturated double-bond structure.Vertical combustion UL-94 highest level reaches V-1~V-0 grades after obtained flame-retardant agent of the present invention is used for unsaturated polyester resin, limit oxygen index LOI maximum value is 33.0%, and heat release rate peak value PHRR and hot total volume THR is below pure unsaturated polyester (UP) in taper calorimetric test；After obtained flame-retardant agent of the present invention is applied to unsaturated polyester glass fibre composite material, vertical combustion UL-94 highest level reaches V1-V-0 grades, and limit oxygen index LOI maximum value is 40%.The flame retardant property of response type phosphonium flame retardant of the present invention is good, influences on material mechanical performance small.The present invention also provides the preparation methods of the fire retardant, and method is simple, and mild condition is easily controllable.
Description
Technical field
The invention belongs to flame retardant areas, and in particular to a kind of response type phosphonium flame retardant and its system
Preparation Method and application.
Background technique
High molecular material due to its abundance, easy processing molding, superior performance, it is cheap many advantages, such as, and
It is widely used in the daily lifes such as space flight and aviation, household electrical appliance, electronic information, building field.But most of macromolecules
Material is all combustible material, is easy to lead to fire, causes heavy losses to the lives and properties of the mankind.Therefore, how high score is reduced
The combustibility of sub- material has become the technology and society problem of people's growing interest.Addition fire retardant is modified it at present
It is to confer to one of the important channel of these high molecular material excellent flame retardancies, this is also provided extensively for the research and development of fire retardant
Wealthy market.
Phosphorus flame retardant is a based flame retardant of current extensive concern, and common phosphorus series non-halogen fire retardant is mainly phosphate
Class, phosphorous acid esters, phosphonic acid ester, organic phosphate, phosphorous heterocylic compound class.And with the development of application demand, merely
Phosphonium flame retardant can no longer meet requirement, therefore many novel phosphorus-containing synergistic fire retardants come into being, such as phosphorus-nitrogen is fire-retardant
Agent, phosphorus-sulphur fire retardant, phosphorus-silicon fire retardant etc..This based flame retardant is at low cost, resourceful and better heat stability, decomposes temperature
Degree meet the processing temperatures such as common engineering plastics, elastomeric polymeric material requirement, can meet to greatest extent special material and
The requirement of high flame retardant.But these fire retardants are present in polymeric matrix in a manner of physical dispersion etc., therefore are existed and added
Dosage is big, and compatibility is poor between polymeric substrate, in process fire retardant can occur overflow, decompose phenomena such as to
The problems such as influencing the mechanical property and flame retardant property of polymer material.And reactive flame retardant can be by the side such as being copolymerized and being grafted
Fire-retardant group or element are directly introduced into main polymer chain or side chain by formula, and polymer material can not only be made to reach higher resistance
Fuel efficiency rate, at the same can overcome traditional additive flame retardant bad dispersibility, easily from polymer surfaces migrate or volatilize the characteristics of, it is right
The destruction of polymer physics mechanical performance is smaller, has preferable development prospect.Currently used reactive flame retardant, the overwhelming majority
Belonging to halogen containing flame-retardant, some non-halogen reacting fire-retardant agent synthesis technologies are complicated, and yield is lower, higher cost, which limits
Its application.Chinese patent CN101831082A report research has synthesized a kind of novel reaction type halogen-free synergistic flame retardant agent, and will
It is introduced into low density polyethylene (LDPE) (LLDPE), achieves preferable flame retardant effect.But the method for synthesizing flame retardant it is complicated,
Process flow is cumbersome, and which limits its industrial applications.
Summary of the invention
In view of the shortcomings of the prior art, described fire-retardant the purpose of the present invention is to provide a kind of response type phosphonium flame retardant
Shown in the general structure of agent such as formula (I):
In general formula (I), A is that the carbon atom number of the linear chain or branched chain containing at least one carbon-carbon double bond is any in 1~10
Alkyl, amino, alkoxy or the alkylthio group of integer, or for the carbon atom number containing at least one carbon-carbon double bond be in 1~20
The alkyl substituting aromatic base or alkyl substituted aryloxy of any integer, or be for the carbon atom number containing at least one carbon-carbon double bond
The ester group of any integer in 1~10；
X, it is-HN-R-NH- ,-HN-R that Y is independent1-NH-、-HN-R1-M-R2-NH-、 -S-R-S-、-S-R1-
S-、-S-R1-M-R2-S-、-O-R-O-、-O-R1-O-、-O-R1-M-R2-O-、 -O-R1-R2-O-、-HN-R1-O-、-HN-R1-M-
R2-O-、-HN-R1-R2-O-、-S-R-S-、 -S-R1-NH-、-S-R1-M-R2-NH-、-S-R1-R2-NH-、-S-R1-OH-、-S-
R1-M-R2- OH- or-S-R1-R2-OH-；
Wherein, R1、R2Independent is phenyl or substituted phenyl；
M represents alkyl, cyclohexyl, the amino that carbon atom number replaces as the linear chain or branched chain of any integer in 1~10 and replaces
Alkyl, sulfuryl, azo group, carbonyl, (CH3)2Si-、(C6H4)2Si-、Substituted phenyl, sulphur atom
Or oxygen atom；
Wherein, shown in the general structure of R such as formula (II):
In general formula (II), R' is the linear or branched alkyl group that carbon atom number is any integer in 1~5, R1'、R2'、R3'、
R4' independent for methyl or phenyl；M is the integer in 1~10 range.
For example, A can be CH2=CH-O-, CH2=C (CH3)-(CH2)2-O-、 CH2=C (CH3)-O-、CH2=C
(CH3)-CH2-O-、C(CH3)2=CH-CH2-O-、 CH2=CH-, CH2=C (CH3)-、CH2=C (CH3)-(CH2)2-、C
(CH3)2=CH-CH2-、One of.
Response type phosphonium flame retardant provided by the invention is drawn on the basis of A expression is containing unsaturated double-bond structure
(I) is entered, the phosphate ester-containing and phosphamide structural unit that (II) indicates.According to test, hang down after being used for unsaturated polyester resin
It is up to V-1~V-0 grades that direct combustion, which burns UL-94 grade, and limit oxygen index LOI maximum value is 33.0%, and peak value is tested in taper calorimetric
Heat release rate peak value PHRR and hot total volume THR are below pure unsaturated polyester (UP).
In addition, after above-mentioned resulting fire retardant is applied to unsaturated polyester glass fibre composite material, vertical combustion UL-94 highest
Grade reaches V1-V-0 grades, and limit oxygen index LOI maximum value is 40%.
Response type phosphonium flame retardant disclosed by the invention can be reacted by unsaturated double-bond functional group with polymer material
For Intrinsical fire proofing, flame retardant property is good, is not easy to migrate from polymeric outer surface, reduces and bring to material mechanical performance
Negative effect.
Another object of the present invention is that providing the preparation method of above-mentioned response type phosphonium flame retardant, method includes
Following steps:
(1) under nitrogen atmosphere, at not higher than 5 DEG C, phosphorus oxychloride is dissolved in organic solvent and is mixed, keep temperature not
Become, is slowly added to above-mentioned A after acid binding agent is added, insulation reaction 4~for 24 hours；
(2) to step (1) gains be added acid binding agent after be slowly added to raw material 3, then in 60~120 DEG C react 4~
For 24 hours, after being washed, being dried to obtained solid to get；
Raw material 3 is H2N-R-NH2、H2N-R1-NH2、H2N-R1-M-R2-NH2、HS-R-SH、 HS-R1-SH、HS-R1-M-R2-
SH、HO-R-OH、HO-R1-OH、HO-R1-M-R2-OH、 HO-R1-R2-OH、H2N-R1-OH、H2N-R1-M-R2-OH、H2N-R1-
R2-OH、 HS-R-SH、HS-R1-NH2、HS-R1-M-R2-NH2、HS-R1-R2-NH2、HS-R1-OH、 HS-R1-M-R2- OH or HS-
R1-R2-OH；Wherein, R, R1、R2Text as defined above is described consistent.
For the sake of facilitating practical operation, the temperature in step (1) is -15~5 DEG C, preferably -5~0 DEG C.
Preferably, in step (1), the molar ratio of acid binding agent and phosphorus oxychloride is 1~4:1；It is furthermore preferred that acid binding agent and three
The molar ratio of chlorethoxyfos is 1~3.5:1.
Preferably, in step (1), the molar ratio of phosphorus oxychloride and the A are 1~1.5:1, it is furthermore preferred that phosphorus oxychloride
Molar ratio with the A is 1~1.25:1.
Preferably, in step (2), the molar ratio of the acid binding agent of addition and the A are 1~2:1；The raw material 3 and A
Molar ratio be 1~1.5:1.
The organic solvent is acetonitrile, tetrahydrofuran, dimethyl sulfoxide, 1-Methyl-2-Pyrrolidone, N, N- dimethyl methyl
At least one of amide, DMAC N,N' dimethyl acetamide, methylene chloride.Those skilled in the art should know, all to dissolve this
It invents the substance and can provide the organic solvent of reaction condition, all belong to the scope of protection of the present invention.
The acid binding agent is triethylamine or pyridine.Those skilled in the art should know that acid binding agent of the present invention is not limited to
State two kinds, it is all to be suitable for acid binding agent of the invention and all belong to the scope of protection of the present invention.
Another object of the present invention also resides in the resulting response type phosphonium flame retardant of the offer present invention in flame retardant area
In application for example can be used as epoxy acrylic resin and/or unsaturated polyester resin and unsaturated polyester glass
The fire retardant of fiber composite material.
The unsaturated polyester glass fibre includes long glass fibres, short glass fiber, glass-fiber-fabric, at least one in glass felt
Kind.Preferably, glass fibre used in unsaturated polyester glass fibre composite material is glass-fiber-fabric.
Compared with prior art, the invention has the following beneficial effects:
1, response type phosphonium flame retardant provided by the invention is as a kind of new reactive flame retardant and high molecular material base
Compatability is not good, easy to migrate, has excellent durability；
2, response type phosphonium flame retardant provided by the invention contains phosphorus, nitrogen, phosphorus, sulphur, and the elements such as phosphorus, silicon are hindered using collaboration
Firing principle has better fireproofing function to substrate, and is halogen-free and has the advantages that low toxicity, is good for the environment；
3, response type phosphonium flame retardant preparation method provided by the invention is simple, and mild condition is easily controllable；
4, response type phosphonium flame retardant provided by the invention has wide range of applications, and can be suitable for epoxy resin, insatiable hunger simultaneously
With multiple polymers system and the unsaturated polyester glass fibre composite material such as polyester resin, and it can reach good fire-retardant effect
Fruit.
Detailed description of the invention
The infrared transform infrared spectrum of the Fourier that Fig. 1 is response type phosphonium flame retardant FR-1 prepared by the embodiment of the present invention 1
Scheme (pellet technique sample preparation)；3418cm in figure-1It is the stretching vibration absworption peak of parahelium N-H, 1734cm-1It is stretching for C=O
Contracting vibration peak, 1636cm-1It is the stretching vibration absworption peak of C=C, 1166cm-1It is the stretching vibration absworption peak of P=O, 1027cm-1
It is-P-N stretching vibration absworption peak；
Fig. 2 is that response type phosphonium flame retardant FR-1 prepared by embodiment 1 is introduced into taper calorimetric survey in unsaturated polyester (UP)
Heat release rate-time plot after examination；
Fig. 3 is that response type phosphonium flame retardant FR-1 prepared by embodiment 1 is introduced into taper calorimetric survey in unsaturated polyester (UP)
Hot total volume-time plot after examination.
Specific embodiment
Embodiment is given below so that the invention will be further described.It is necessarily pointed out that following embodiment is not
It can be interpreted as limiting the scope of the invention, if the person skilled in the art in the field is according to aforementioned present invention content to this
Some nonessential modifications and adaptations are made in invention, still fall within the scope of the present invention.
Embodiment 1
First under nitrogen protection, 0.2mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.6mol triethylamine, be then slowly added dropwise in 2h 50mL tetrahydrofuran dissolution
0.2mol hydroxy-ethyl acrylate, the reaction was continued at such a temperature after being added dropwise 6h, obtain containing double bond structure monosubstituted contains
Phosphorus intermediate (III) solution.0.2mol triethylamine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature,
Then the 0.2mol 4 of 60mL tetrahydrofuran dissolution, 4- diaminodiphenyl ether, by solution after being added dropwise are slowly added dropwise in 2h
Temperature rises to 100 DEG C of reaction 8h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized water
It washs 3~4 times, just obtains response type phosphonium flame retardant FR-1, yield 87.3% after dry.
Embodiment 2
First under nitrogen protection, 0.22mol phosphorus oxychloride is added in 150mL acetonitrile at 0~-10 DEG C and is stirred
It is uniformly mixed, 0.66mol pyridine is then added at such a temperature, the dissolution of 50mL acetonitrile is then slowly added dropwise in 1.5h
0.2mol hydroxy-ethyl acrylate, the reaction was continued at such a temperature after being added dropwise 7h are obtained monosubstituted phosphorous containing double bond structure
Intermediate (III) solution.0.2mol pyridine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, then
0.2 mol 4 of 60mL acetonitrile dissolution, 4- diaminodiphenylmethane, by solution temperature liter after being added dropwise are slowly added dropwise in 2h
It to 90 DEG C of reaction 7h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized 3~4
It is secondary, response type phosphonium flame retardant FR-2, yield 85.1% are just obtained after dry.
Embodiment 3
First under nitrogen protection, 0.2mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.7mol triethylamine, be then slowly added dropwise in 2h 50mL tetrahydrofuran dissolution
0.2mol hydroxy-ethyl acrylate, the reaction was continued at such a temperature after being added dropwise 6h, obtain containing double bond structure monosubstituted contains
Phosphorus intermediate (III) solution.0.2mol triethylamine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature,
Then the 0.2mol4 of 60mL tetrahydrofuran dissolution, 4- diaminodiphenyl ether, by solution temperature after being added dropwise are slowly added dropwise in 2h
Degree rises to 85 DEG C of reaction 8h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized
3~4 times, response type phosphonium flame retardant FR-3, yield 86.0% are just obtained after dry.
Embodiment 4
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150mL tetrahydrofuran at 0~-10 DEG C
It is uniformly mixed, 0.75mol triethylamine is then added at such a temperature, it is molten that 60mL tetrahydrofuran is then slowly added dropwise in 3h
The 0.2mol hydroxy-ethyl acrylate of solution, the reaction was continued at such a temperature after being added dropwise 7h are obtained containing the monosubstituted of double bond structure
Phosphorous intermediate (III) solution.0.2mol pyridine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature,
Then the 0.2mol 4 of 60mL tetrahydrofuran dissolution, 4- diaminodiphenylsulfone, by solution after being added dropwise are slowly added dropwise in 2h
Temperature rises to 85 DEG C of reaction 7h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized water
It washs 3~4 times, just obtains response type phosphonium flame retardant FR-4, yield 79.0% after dry.
Embodiment 5
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150mL acetonitrile at 0~-10 DEG C and is stirred
It is uniformly mixed, 0.88mol triethylamine is then added at such a temperature, the dissolution of 50mL acetonitrile is then slowly added dropwise in 1.5h
0.2mol hydroxy-ethyl acrylate, the reaction was continued at such a temperature after being added dropwise 7h are obtained monosubstituted phosphorous containing double bond structure
Intermediate (III) solution.0.3mol triethylamine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, connects
Be slowly added dropwise in 2h 60mL acetonitrile dissolution 0.3 mol 4,4- diaminodiphenylmethane, by solution temperature after being added dropwise
90 DEG C of reaction 7h are risen to, filters remove liquid after reaction, and obtained yellow solid is washed with deionized 3
~4 times, response type phosphonium flame retardant FR-5, yield 89.1% are just obtained after dry.
Embodiment 6
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150 mL methylene chloride at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.8mol pyridine, be then slowly added dropwise in 2.5h 50mL methylene chloride dissolution
0.2mol hydroxy-ethyl acrylate, the reaction was continued at such a temperature after being added dropwise 8h, obtain containing double bond structure monosubstituted contains
Phosphorus intermediate (III) solution.0.22mol pyridine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature,
Then the 0.3mol 4 of 60mL methylene chloride dissolution is slowly added dropwise in 2h, 4- diaminodiphenylmethane will be molten after being added dropwise
Liquid temperature rises to 60 DEG C of reaction 12h, filters remove liquid after reaction, and the yellow solid deionization that will be obtained
Water washing 3~4 times, response type phosphonium flame retardant FR-6, yield 78.0% are just obtained after dry.
Embodiment 7
First under nitrogen protection, 0.24mol phosphorus oxychloride is added in 150 mL dimethyl sulfoxides at 0~-5 DEG C
It is uniformly mixed, 0.77mol triethylamine is then added at such a temperature, 50mL dimethyl sulfoxide is then slowly added dropwise in 2h
The 0.2mol hydroxy-ethyl acrylate of dissolution, the reaction was continued at such a temperature after being added dropwise 6h obtain singly taking containing double bond structure
For phosphorous intermediate (III) solution.0.2mol tri- is added into intermediate obtained in above-mentioned steps (III) solution at room temperature
Ethamine, is then slowly added dropwise the 0.2mol 4 of 60mL dmso solution in 2.5h, and 4- diaminodiphenyl ether is added dropwise
Solution temperature is risen into 110 DEG C of reaction 6h afterwards, filters remove liquid after reaction, and obtained yellow solid is spent
Ion water washing 3~4 times, response type phosphonium flame retardant FR-7, yield 89.5% are just obtained after dry.
Embodiment 8
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150 mL dimethyl sulfoxides at 0~-5 DEG C
It is uniformly mixed, 0.75mol pyridine is then added at such a temperature, it is molten that 60mL dimethyl sulfoxide is then slowly added dropwise in 2h
The 0.2mol hydroxy-ethyl acrylate of solution, the reaction was continued at such a temperature after being added dropwise 6h are obtained containing the monosubstituted of double bond structure
Phosphorous intermediate (III) solution.0.25mol pyrrole is added into intermediate obtained in above-mentioned steps (III) solution at room temperature
The 0.4mol 4 of 60mL dmso solution is then slowly added dropwise in pyridine in 2h, and 4- diaminodiphenyl ether will after being added dropwise
Solution temperature rises to 100 DEG C of reaction 4h, after reaction filter remove liquid, and by obtained yellow solid spend from
Sub- water washing 3~4 times just obtains response type phosphonium flame retardant FR-8, yield 88.3% after dry.
Embodiment 9
First under nitrogen protection, 0.22mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.70mol pyridine, 70mL dmso solution is then slowly added dropwise in 2h
0.2mol hydroxy-ethyl acrylate, the reaction was continued at such a temperature after being added dropwise 7h, obtain containing double bond structure monosubstituted contains
Phosphorus intermediate (III) solution.0.2mol pyridine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, connects
Be slowly added dropwise in 2h 60mL tetrahydrofuran dissolution 0.2mol 4,4- dimercapto diphenyl sulfide, by solution after being added dropwise
Temperature rises to 85 DEG C of reaction 6h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized water
It washs 3~4 times, just obtains response type phosphonium flame retardant FR-9, yield 85.0% after dry.
Embodiment 10
First under nitrogen protection, 0.25mol phosphorus oxychloride is added to 150 mL N, N- dimethyl at 0~-5 DEG C
It is uniformly mixed in formamide, 0.8mol triethylamine is then added at such a temperature, 50mL is then slowly added dropwise in 2h
0.2 mol hydroxy-ethyl acrylate of n,N-Dimethylformamide dissolution, the reaction was continued at such a temperature after being added dropwise 6h are obtained
Monosubstituted phosphorous intermediate (III) solution containing double bond structure.At room temperature to intermediate obtained in above-mentioned steps (III) solution
The 0.4mol 3,3'- of 60mL n,N-Dimethylformamide dissolution is then slowly added dropwise in middle addition 0.3mol triethylamine in 3h
Solution temperature is risen to 120 DEG C of reaction 7h after being added dropwise by diaminobenzophenone, filters remove liquid after reaction
Body, and obtained yellow solid is washed with deionized 3~4 times, response type phosphonium flame retardant FR-10 is just obtained after dry,
Yield 89.0%.
Embodiment 11
First under nitrogen protection, 0.25mol phosphorus oxychloride is added to 150 mL N, N- dimethyl at 0~-5 DEG C
It is uniformly mixed in acetamide, 0.6mol triethylamine is then added at such a temperature, 50mL is then slowly added dropwise in 2h
0.2 mol hydroxy-ethyl acrylate of n,N-dimethylacetamide dissolution, the reaction was continued at such a temperature after being added dropwise 6h are obtained
Monosubstituted phosphorous intermediate (III) solution containing double bond structure.At room temperature to intermediate obtained in above-mentioned steps (III) solution
60mLN, the 0.25mol 3,3'- of N- dimethyl acetamide dissolution is then slowly added dropwise in middle addition 0.25mol pyridine in 3h
Solution temperature is risen to 120 DEG C of reaction 6h after being added dropwise by diaminobenzophenone, filters remove liquid after reaction
Body, and obtained yellow solid is washed with deionized 3~4 times, response type phosphonium flame retardant FR-11 is just obtained after dry,
Yield 91.0%.
Embodiment 12
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.75mol pyridine, 70mL dmso solution is then slowly added dropwise in 2h
0.2mol hydroxy-ethyl acrylate, the reaction was continued at such a temperature after being added dropwise 6h, obtain containing double bond structure monosubstituted contains
Phosphorus intermediate (III) solution.0.3mol pyridine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, connects
Be slowly added dropwise in 2h 60mL tetrahydrofuran dissolution 0.2mol 4,4- dimercapto diphenyl sulfide, by solution after being added dropwise
Temperature rises to 70 DEG C of reaction 8h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized water
It washs 3~4 times, just obtains response type phosphonium flame retardant FR-12,75.0% embodiment 13 of yield after dry
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150mL tetrahydrofuran at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.8mol triethylamine, be then slowly added dropwise in 2h 60mL tetrahydrofuran dissolution
0.2mol 4-Vinyl phenol, the reaction was continued at such a temperature after being added dropwise 7h, obtain containing double bond structure monosubstituted contains
Phosphorus intermediate (III) solution.Tri- second of 0.25mol is added into intermediate obtained in above-mentioned steps (III) solution at room temperature
The 0.26mol 4 of 70mL tetrahydrofuran dissolution, 4- diaminodiphenylmethane, after being added dropwise then is slowly added dropwise in amine in 2h
Solution temperature is risen into 70 DEG C of reaction 6h, after reaction filter remove liquid, and by obtained yellow solid spend from
Sub- water washing 3~4 times just obtains response type phosphonium flame retardant FR-13, yield 78.0% after dry.
Embodiment 14
First under nitrogen protection, 0.2mol phosphorus oxychloride is added in 150 mL dimethyl sulfoxides at 0~-10 DEG C
It is uniformly mixed, 0.6mol triethylamine is then added at such a temperature, 60mL dimethyl sulfoxide is then slowly added dropwise in 3h
The 0.2mol 4-Vinyl phenol of dissolution, the reaction was continued at such a temperature after being added dropwise 7h obtain singly taking containing double bond structure
For phosphorous intermediate (III) solution.0.2mol tri- is added into intermediate obtained in above-mentioned steps (III) solution at room temperature
The 0.2mol 4 of 70mL dmso solution, 4- diaminodiphenyl ether, after being added dropwise then is slowly added dropwise in ethamine in 2h
Solution temperature is risen into 120 DEG C of reaction 9h, filters remove liquid after reaction, and obtained yellow solid is spent
Ion water washing 3~4 times, response type phosphonium flame retardant FR-14, yield 88.5% are just obtained after dry.
Embodiment 15
First under nitrogen protection, 0.22mol phosphorus oxychloride is added in 150 mL methylene chloride at 0~-10 DEG C
It is uniformly mixed, 0.75mol pyridine is then added at such a temperature, 70mL dimethyl sulfoxide is then slowly added dropwise in 1.5h
The 0.2mol 4-Vinyl phenol of dissolution, the reaction was continued at such a temperature after being added dropwise 7h obtain singly taking containing double bond structure
For phosphorous intermediate (III) solution.0.2mol pyrrole is added into intermediate obtained in above-mentioned steps (III) solution at room temperature
The 0.22mol 4 of 70mL methylene chloride dissolution is then slowly added dropwise in pyridine in 2h, and 4- diaminodiphenylsulfone will after being added dropwise
Solution temperature rises to 60 DEG C of reaction 12h, filters remove liquid after reaction, and the yellow solid deionization that will be obtained
Water washing 3~4 times, response type phosphonium flame retardant FR-15, yield 77.3% are just obtained after dry.
Embodiment 16
First under nitrogen protection, 0.24mol phosphorus oxychloride is added to 150mL N, N- dimethyl at 0~-10 DEG C
It is uniformly mixed in formamide, 0.72mol triethylamine is then added at such a temperature, 60mL is then slowly added dropwise in 3h
The 0.2mol 1- amino -3- methyl-2-butene of n,N-Dimethylformamide dissolution continues anti-at such a temperature after being added dropwise
7h is answered, monosubstituted phosphorous intermediate (III) solution containing double bond structure is obtained.At room temperature to intermediate obtained in above-mentioned steps
0.3mol triethylamine is added in body (III) solution, 70mLN is then slowly added dropwise in 2.5h, dinethylformamide dissolution
Solution temperature is risen to 110 DEG C of reaction 7h after being added dropwise, after reaction by 0.3mol 3,3'- diaminobenzophenone
It filters and removes liquid, and obtained yellow solid is washed with deionized 3~4 times, just obtain the phosphorous resistance of response type after dry
Fire agent FR-16, yield 88.5%.
Embodiment 17
First under nitrogen protection, 0.22mol phosphorus oxychloride is added to stir in 150mL acetonitrile at 0~-5 DEG C and is mixed
It closes uniformly, 0.77mol triethylamine is then added at such a temperature, the dissolution of 60mL acetonitrile is then slowly added dropwise in 2.5h
0.2mol 1- amino -3- methyl -2- butylene, the reaction was continued at such a temperature after being added dropwise 6h are obtained containing double bond structure
Monosubstituted phosphorous intermediate (III) solution.It is added at room temperature into intermediate obtained in above-mentioned steps (III) solution
The 0.30mol 3 of 70mL acetonitrile dissolution, 3'- diaminobenzophenone, drop is then slowly added dropwise in 0.25mol triethylamine in 3h
Solution temperature is risen into 80 DEG C of reaction 8h after adding, filters remove liquid after reaction, and obtained yellow is consolidated
Body is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-17, yield 76.9% after dry.
Embodiment 18
First under nitrogen protection, 0.2mol phosphorus oxychloride is added in 150 mL methylene chloride at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.6mol triethylamine, it is molten that 60mL methylene chloride is then slowly added dropwise in 2.5h
The 0.2mol 1- amino -3- methyl-2-butene of solution, the reaction was continued at such a temperature after being added dropwise 8h are obtained containing double bond structure
Monosubstituted phosphorous intermediate (III) solution.It is added at room temperature into intermediate obtained in above-mentioned steps (III) solution
The 0.2mol 4 of 70mL methylene chloride dissolution, 4- dimercapto diphenyl sulfide, drop is then slowly added dropwise in 0.2mol triethylamine in 2h
Solution temperature is risen into 90 DEG C of reaction 9h after adding, filters remove liquid after reaction, and obtained yellow is consolidated
Body is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-18, yield 87.0% after dry.
Embodiment 19
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.6mol pyridine, be then slowly added dropwise in 2.5h 60mL tetrahydrofuran dissolution
0.2mol 1- amino -3- methyl-2-butene, the reaction was continued at such a temperature after being added dropwise 8h obtains containing double bond structure
Monosubstituted phosphorous intermediate (III) solution.It is added at room temperature into intermediate obtained in above-mentioned steps (III) solution
0.3mol pyridine, is then slowly added dropwise the 0.25mol 4 of 70mL tetrahydrofuran dissolution in 2h, and 4- diaminodiphenylsulfone is added dropwise
After solution temperature risen into 80 DEG C of reaction 8h, filter remove liquid after reaction, and the yellow solid that will be obtained
It is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-19, yield 87.4% after dry.
Embodiment 20
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.6mol pyridine, be then slowly added dropwise in 2.5h 60mL tetrahydrofuran dissolution
0.2mol 1- amino -3- methyl-2-butene, the reaction was continued at such a temperature after being added dropwise 8h obtains containing double bond structure
Monosubstituted phosphorous intermediate (III) solution.It is added at room temperature into intermediate obtained in above-mentioned steps (III) solution
0.3mol pyridine, is then slowly added dropwise the 0.25mol 4 of 70mL tetrahydrofuran dissolution in 2h, and 4- diaminodiphenylsulfone is added dropwise
After solution temperature risen into 80 DEG C of reaction 8h, filter remove liquid after reaction, and the yellow solid that will be obtained
It is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-20, yield 87.4% after dry.
Embodiment 21
First under nitrogen protection, 0.22mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.66mol triethylamine, be then slowly added dropwise in 2h 60mL tetrahydrofuran dissolution
0.2mol propylene mercaptan, the reaction was continued at such a temperature after being added dropwise 7h, obtain containing double bond structure it is monosubstituted it is phosphorous in
Mesosome (III) solution.0.4mol triethylamine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, then
The 0.26mol 4 of 70mL tetrahydrofuran dissolution, 4- diaminodiphenylmethane, by solution after being added dropwise are slowly added dropwise in 2h
Temperature rises to 70 DEG C of reaction 6h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized water
It washs 3~4 times, just obtains response type phosphonium flame retardant FR-21, yield 88.7% after dry.
Embodiment 22
First under nitrogen protection, 0.22mol phosphorus oxychloride is added in 150 mL methylene chloride at 0~-10 DEG C
It is uniformly mixed, 0.75mol pyridine is then added at such a temperature, 70mL dimethyl sulfoxide is then slowly added dropwise in 1.5h
The 0.2mol propylene mercaptan of dissolution, the reaction was continued at such a temperature after being added dropwise 7h, obtain containing double bond structure monosubstituted contains
Phosphorus intermediate (III) solution.0.2mol pyridine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, connects
Be slowly added dropwise in 2h 70mL methylene chloride dissolution 0.22mol 4,4- diaminodiphenylsulfone, by solution after being added dropwise
Temperature rises to 60 DEG C of reaction 12h, filters remove liquid after reaction, and the yellow solid deionized water that will be obtained
Washing 3~4 times just obtains response type phosphonium flame retardant FR-22, yield 87.3% after dry.
Embodiment 23
First under nitrogen protection, 0.2mol phosphorus oxychloride is added in 150 mL methylene chloride at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.6mol triethylamine, it is molten that 60mL methylene chloride is then slowly added dropwise in 2.5h
The 0.2mol propylene mercaptan of solution, the reaction was continued at such a temperature after being added dropwise 8h are obtained monosubstituted phosphorous containing double bond structure
Intermediate (III) solution.0.2mol triethylamine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, connects
Be slowly added dropwise in 2h 70mL methylene chloride dissolution 0.2mol 4,4- dimercapto diphenyl sulfide, by solution after being added dropwise
Temperature rises to 65 DEG C of reaction 11h, filters remove liquid after reaction, and obtained yellow solid is washed with deionized water
It washs 3~4 times, just obtains response type phosphonium flame retardant FR-23, yield 87.0% after dry.
Embodiment 24
First under nitrogen protection, 0.25mol phosphorus oxychloride is added to 150 mL N, N- dimethyl at 0~-5 DEG C
It is uniformly mixed in formamide, 0.8mol triethylamine is then added at such a temperature, 50mL is then slowly added dropwise in 2h
0.2 mol propylene mercaptan of n,N-Dimethylformamide dissolution, the reaction was continued at such a temperature after being added dropwise 6h are obtained containing double
Monosubstituted phosphorous intermediate (III) solution of bond structure.Add at room temperature into intermediate obtained in above-mentioned steps (III) solution
Enter 0.3mol triethylamine, the 0.26mol 3 of 60mL n,N-Dimethylformamide dissolution, 3'- diamino are then slowly added dropwise in 3h
Solution temperature is risen to 120 DEG C of reaction 6h after being added dropwise by base benzophenone, filters remove liquid after reaction, and
Obtained yellow solid is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-24, yield after dry
89.0%.
Embodiment 25
First under nitrogen protection, 0.2mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.6mol pyridine, be then slowly added dropwise in 2h 50mL tetrahydrofuran dissolution
0.2mol propylene mercaptan, the reaction was continued at such a temperature after being added dropwise 6h obtain the monosubstituted phosphorous centre containing double bond structure
Body (III) solution.0.2mol pyridine is added into intermediate obtained in above-mentioned steps (III) solution at room temperature, then in 2h
0.2 mol 4 of 60mL tetrahydrofuran dissolution is inside slowly added dropwise, 4- diaminodiphenyl ether rises to solution temperature after being added dropwise
90 DEG C of reaction 8h are filtered remove liquid after reaction, and obtained yellow solid is washed with deionized 3~4
It is secondary, response type phosphonium flame retardant FR-25, yield 86.7% are just obtained after dry.
Embodiment 26
First under nitrogen protection, 0.25mol phosphorus oxychloride is added to 150 mL N, N- dimethyl at 0~-5 DEG C
It is uniformly mixed in acetamide, 0.6mol triethylamine is then added at such a temperature, 50mL is then slowly added dropwise in 2h
0.2 mol propylene mercaptan of n,N-dimethylacetamide dissolution, the reaction was continued at such a temperature after being added dropwise 6h are obtained containing double
Monosubstituted phosphorous intermediate (III) solution of bond structure.Add at room temperature into intermediate obtained in above-mentioned steps (III) solution
Enter 0.25mol pyridine, the 0.25mol 3 of 60mL n,N-dimethylacetamide dissolution, 3'- diamino are then slowly added dropwise in 3h
Solution temperature is risen to 120 DEG C of reaction 5h after being added dropwise by base benzophenone, filters remove liquid after reaction, and
Obtained yellow solid is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-26, yield after dry
89.0%.
Embodiment 27
First under nitrogen protection, 0.22mol phosphorus oxychloride is added in 150mL acetonitrile at 0~-10 DEG C and is stirred
It is uniformly mixed, 0.66mol pyridine is then added at such a temperature, the dissolution of 50mL acetonitrile is then slowly added dropwise in 1.5h
0.2mol methacrylic acid β-hydroxypropyl acrylate, the reaction was continued at such a temperature after being added dropwise 7h, obtain singly taking containing double bond structure
For phosphorous intermediate (III) solution.0.2mol pyrrole is added into intermediate obtained in above-mentioned steps (III) solution at room temperature
The 0.2mol 4 of 60mL acetonitrile dissolution is then slowly added dropwise in pyridine in 2h, and 4- diaminodiphenylmethane will be molten after being added dropwise
Liquid temperature rises to 90 DEG C of reaction 7h, filters remove liquid after reaction, and the yellow solid deionized water that will be obtained
Washing 3~4 times just obtains response type phosphonium flame retardant FR-27, yield 85.1% after dry.
Embodiment 28
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150 mL tetrahydrofurans at 0~-5 DEG C and is stirred
Mix it is uniformly mixed, then at such a temperature be added 0.75mol pyridine, 70mL dmso solution is then slowly added dropwise in 2h
0.2mol methacrylic acid β-hydroxypropyl acrylate, the reaction was continued at such a temperature after being added dropwise 6h obtains the list containing double bond structure
Replace phosphorous intermediate (III) solution.0.3mol is added into intermediate obtained in above-mentioned steps (III) solution at room temperature
The 0.3mol 4 of 60mL tetrahydrofuran dissolution, 4- dimercapto diphenyl sulfide, after being added dropwise then is slowly added dropwise in pyridine in 2h
Solution temperature is risen into 70 DEG C of reaction 8h, after reaction filter remove liquid, and by obtained yellow solid spend from
Sub- water washing 3~4 times just obtains response type phosphonium flame retardant FR-28, yield 85.0% after dry
Embodiment 29
First under nitrogen protection, 0.25mol phosphorus oxychloride is added in 150 mL dimethyl sulfoxides at 0~-5 DEG C
It is uniformly mixed, 0.75mol pyridine is then added at such a temperature, it is molten that 60mL dimethyl sulfoxide is then slowly added dropwise in 2h
0.2mol methacrylic acid β-hydroxypropyl acrylate of solution, the reaction was continued at such a temperature after being added dropwise 6h are obtained containing double bond structure
Monosubstituted phosphorous intermediate (III) solution.It is added at room temperature into intermediate obtained in above-mentioned steps (III) solution
The 0.25mol 4 of 60mL dmso solution, 4- diaminodiphenyl ether, drop is then slowly added dropwise in 0.25mol pyridine in 2h
Solution temperature is risen into 120 DEG C of reaction 6h after adding, filters remove liquid after reaction, and obtained yellow is consolidated
Body is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-29, yield 88.3% after dry.
Embodiment 30
First under nitrogen protection, 0.22mol phosphorus oxychloride is added in 150mL methylene chloride at 0~-10 DEG C
It is uniformly mixed, 0.75mol pyridine is then added at such a temperature, 70mL dimethyl sulfoxide is then slowly added dropwise in 1.5h
0.2mol methacrylic acid β-hydroxypropyl acrylate of dissolution, the reaction was continued at such a temperature after being added dropwise 7h are obtained containing double bond structure
Monosubstituted phosphorous intermediate (III) solution.It is added at room temperature into intermediate obtained in above-mentioned steps (III) solution
0.2mol pyridine, is then slowly added dropwise the 0.22mol 4 of 70mL methylene chloride dissolution in 2h, and 4- diaminodiphenylsulfone is added dropwise
After solution temperature risen into 60 DEG C of reaction 12h, filter remove liquid after reaction, and the yellow solid that will be obtained
It is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-30, yield 87.3% after dry.
Embodiment 31
First under nitrogen protection, 0.25mol phosphorus oxychloride is added to 150 mL N, N- dimethyl at 0~-5 DEG C
It is uniformly mixed in formamide, 0.8mol triethylamine is then added at such a temperature, 50mL is then slowly added dropwise in 2h
0.2 mol propylene mercaptan of n,N-Dimethylformamide dissolution, the reaction was continued at such a temperature after being added dropwise 6h are obtained containing double
Monosubstituted phosphorous intermediate (III) solution of bond structure.Add at room temperature into intermediate obtained in above-mentioned steps (III) solution
Enter 0.3mol triethylamine, the 0.26mol 3 of 60mL n,N-Dimethylformamide dissolution, 3'- diamino are then slowly added dropwise in 3h
Solution temperature is risen to 120 DEG C of reaction 6h after being added dropwise by base benzophenone, filters remove liquid after reaction, and
Obtained yellow solid is washed with deionized 3~4 times, just obtains response type phosphonium flame retardant FR-31, yield after dry
89.0%.
Embodiment 32
In order to examine or check the flame retardant effect of the obtained response type phosphonium flame retardant of the present invention in the polymeric material, the present embodiment choosing
Use a kind of common combustible polymers material-unsaturated polyester resin (UPR) as matrix, by fire retardant obtained by matching below
Side's (being shown in Table 1) is added in unsaturated polyester (UP), on vulcanizing press 80 DEG C it is hot-forming and machine cuts obtain standard sample
Item (batten specification, limit oxygen index (LOI): 120mm × 6.5mm × 3.2mm；Vertical combustion (UL-94): 130mm × 13mm ×
3.2mm；Taper calorimetric (Cone) test: 100mm × 100mm × 3.2mm), to these samples and plus fire retardant it is pure not
Saturated polyester carries out flame retardant property and is tested.(combustion testing reference standard: LOI test: ASTM D2863-97；UL-94 is surveyed
Examination: ASTM D3801-10；Cone test: ISO 5660).
The component prescription and test result of 1 standard sample of table
Embodiment 33
In order to examine or check the flame retardant effect of the obtained response type phosphonium flame retardant of the present invention in the composite, the present embodiment will be made
Standby obtained fire retardant, unsaturated polyester resin and glass-fiber-fabric is carried out compound with different formulations (being shown in Table 2).Using hand paste at
Type, simultaneously machine cuts obtain flameproof unsaturated polyester glass fiber composite material standard batten (sample for 80 DEG C of hot pressing on vulcanizing press
Specification, limit oxygen index (LOI): 120mm × 6.5mm × 3.2mm；Vertical combustion (UL-94): 130mm × 13mm ×
3.2mm；Taper calorimetric (Cone) test: 100 mm × 100mm × 3.2mm).To these samples and plus fire retardant it is pure not
Saturated polyester glass fiber composite material carries out flame retardant property and is tested.(combustion testing reference standard: LOI test: ASTM
D2863-97；UL-94 test: ASTM D3801-10；Cone test: ISO 5660).
The component prescription and test result of 2 standard sample of table
As can be known from Table 1, fire retardant of the present invention is up to for vertical combustion UL-94 grade after unsaturated polyester resin
To V-1~V-0 grades, limit oxygen index LOI maximum value is 33.0%.
As can be known from Table 2, fire retardant of the present invention is for after unsaturated polyester glass fibre composite material, vertical combustion UL-94 to be most
High-grade to reach V1-V-0 grades, limit oxygen index LOI maximum value is 40.0%,
As shown in Figure 2, response type phosphonium flame retardant FR-1 prepared by the embodiment of the present invention 1 is introduced into unsaturated polyester (UP) tree
After in rouge, its heat release rate peak value is significantly reduced, heat release rate has been delayed, improves the anti-flammability of material.
From the figure 3, it may be seen that response type phosphonium flame retardant FR-1 prepared by the embodiment of the present invention 1 is introduced into unsaturated polyester (UP) tree
After in rouge, its total heat release is significantly reduced.
Claims (10)
1. a kind of response type phosphonium flame retardant, which is characterized in that shown in the general structure of the fire retardant such as formula (I):
In general formula (I), A is that the carbon atom number of the linear chain or branched chain containing at least one carbon-carbon double bond is any integer in 1~10
Alkyl, amino, alkoxy or alkylthio group, or for the carbon atom number containing at least one carbon-carbon double bond be in 1~20 it is any
The alkyl substituting aromatic base or alkyl substituted aryloxy of integer, or for the carbon atom number containing at least one carbon-carbon double bond be 1~
The ester group of any integer in 10；
X, it is-HN-R-NH- ,-HN-R that Y is independent1-NH-、-HN-R1-M-R2-NH-、-S-R-S-、-S-R1-S-、-S-R1-
M-R2-S-、-O-R-O-、-O-R1-O-、-O-R1-M-R2-O-、-O-R1-R2-O-、-HN-R1-O-、-HN-R1-M-R2-O-、-HN-
R1-R2-O-、-S-R-S-、-S-R1-NH-、-S-R1-M-R2-NH-、-S-R1-R2-NH-、-S-R1-OH-、-S-R1-M-R2-OH-
Or-S-R1-R2-OH-；
Wherein, R1、R2Independent is phenyl or substituted phenyl；
M represents the alkane that alkyl, cyclohexyl, the amino that carbon atom number replaces as the linear chain or branched chain of any integer in 1~10 replace
Base, sulfuryl, azo group, carbonyl, (CH3)2Si-、(C6H4)2Si-、Substituted phenyl, sulphur atom or oxygen
Atom；
Wherein, shown in the general structure of R such as formula (II):
In general formula (II), R' is the linear or branched alkyl group that carbon atom number is any integer in 1~5, R1'、R2'、R3'、R4' respectively
It is independently methyl or phenyl；M is the integer in 1~10 range.
2. response type phosphonium flame retardant according to claim 1, which is characterized in that A CH2=CH-O-, CH2=C
(CH3)-(CH2)2-O-、CH2=C (CH3)-O-、CH2=C (CH3)-CH2-O-、C(CH3)2=CH-CH2-O-、CH2=CH-, CH2
=C (CH3)-、CH2=C (CH3)-(CH2)2-、C(CH3)2=CH-CH2-、In
It is a kind of.
3. the preparation method of response type phosphonium flame retardant of any of claims 1 or 2, which is characterized in that the method includes with
Lower step:
(1) under nitrogen atmosphere, at not higher than 5 DEG C, phosphorus oxychloride is dissolved in organic solvent and is mixed, keep temperature-resistant,
A as claimed in claim 1 or 2 is slowly added to after acid binding agent is added, insulation reaction 4~for 24 hours；
(2) to step (1) gains be added acid binding agent after be slowly added to raw material 3, then in 60~120 DEG C react 4~for 24 hours, it is right
Obtained solid washed, dried after to get；
Raw material 3 is H2N-R-NH2、H2N-R1-NH2、H2N-R1-M-R2-NH2、HS-R-SH、HS-R1-SH、HS-R1-M-R2-SH、
HO-R-OH、HO-R1-OH、HO-R1-M-R2-OH、HO-R1-R2-OH、H2N-R1-OH、H2N-R1-M-R2-OH、H2N-R1-R2-OH、
HS-R-SH、HS-R1-NH2、HS-R1-M-R2-NH2、HS-R1-R2-NH2、HS-R1-OH、HS-R1-M-R2- OH or HS-R1-R2-
OH；Wherein, R, R1、R2With described in claim 1.
4. preparation method according to claim 3, which is characterized in that the temperature in step (1) is -15~5 DEG C, preferably
It is -5~0 DEG C.
5. preparation method according to claim 3, which is characterized in that in step (1), mole of acid binding agent and phosphorus oxychloride
Than 1~4:1, preferably 1~3.5:1.
6. according to the described in any item preparation methods of claim 3~5, which is characterized in that in step (1), phosphorus oxychloride and institute
The molar ratio for stating A is 1~1.5:1, preferably 1~1.25:1.
7. preparation method according to claim 6, which is characterized in that in step (2), the acid binding agent of addition is with the A's
Molar ratio is 1~2:1；The molar ratio of the raw material 3 and A is 1~1.5:1.
8. according to the described in any item preparation methods of claim 3~7, which is characterized in that the organic solvent is acetonitrile, tetrahydro
Furans, dimethyl sulfoxide, 1-Methyl-2-Pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, methylene chloride
At least one of.
9. the preparation method according to claim 3~7, which is characterized in that the acid binding agent is triethylamine or pyridine.
10. response type of any of claims 1 or 2 or being prepared by any one of claim 3~9 preparation method
Application of the phosphonium flame retardant in flame retardant area, the application include being used as epoxy acrylic resin and/or unsaturated polyester (UP) tree
Rouge fire retardant, or as fire-retardant dose of unsaturated polyester glass fibre composite material, the unsaturated polyester glass fibre include long glass fibres,
At least one of short glass fiber, glass-fiber-fabric, glass felt, preferably glass-fiber-fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710361025.8A CN108948424B (en) | 2017-05-19 | 2017-05-19 | Reactive phosphorus-containing flame retardant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710361025.8A CN108948424B (en) | 2017-05-19 | 2017-05-19 | Reactive phosphorus-containing flame retardant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108948424A true CN108948424A (en) | 2018-12-07 |
| CN108948424B CN108948424B (en) | 2020-12-11 |
Family
ID=64463062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710361025.8A Active CN108948424B (en) | 2017-05-19 | 2017-05-19 | Reactive phosphorus-containing flame retardant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108948424B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480319A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Acrylamide copolymer and preparation method and application thereof |
| CN112480677A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Silicon rubber composition and preparation method and application thereof |
| CN113512284A (en) * | 2021-04-27 | 2021-10-19 | 骏能化工（龙南）有限公司 | Preparation method of high-flame-retardant polyurethane composite material |
| CN113801320A (en) * | 2020-06-01 | 2021-12-17 | 中国石油化工股份有限公司 | Bio-based block polymer, preparation method and application thereof, flame-retardant compound and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5412138A (en) * | 1990-06-14 | 1995-05-02 | Elf Atochem S.A. | Phosphorus-containing acrylic compounds and polymers thereof |
| CN101597307A (en) * | 2009-07-09 | 2009-12-09 | 中国科学技术大学 | A kind of uV curable phosphorus-nitrogen-containing halogen-free flame retardant and preparation method thereof |
| CN102757580A (en) * | 2012-07-31 | 2012-10-31 | 广东聚石化学股份有限公司 | Reaction type phosphorus-nitrogen fire retardant and synthesizing method thereof |
| CN102942586A (en) * | 2012-11-23 | 2013-02-27 | 张家港顺昌化工有限公司 | Preparation method of 2-ethyl methacrylate benzyl phosphate |
| CN104844804A (en) * | 2015-03-25 | 2015-08-19 | 沈阳化工大学 | Polymer type phosphorus-nitrogen intumescent flame retardant and preparation method therefor |
-
2017
- 2017-05-19 CN CN201710361025.8A patent/CN108948424B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5412138A (en) * | 1990-06-14 | 1995-05-02 | Elf Atochem S.A. | Phosphorus-containing acrylic compounds and polymers thereof |
| CN101597307A (en) * | 2009-07-09 | 2009-12-09 | 中国科学技术大学 | A kind of uV curable phosphorus-nitrogen-containing halogen-free flame retardant and preparation method thereof |
| CN102757580A (en) * | 2012-07-31 | 2012-10-31 | 广东聚石化学股份有限公司 | Reaction type phosphorus-nitrogen fire retardant and synthesizing method thereof |
| CN102942586A (en) * | 2012-11-23 | 2013-02-27 | 张家港顺昌化工有限公司 | Preparation method of 2-ethyl methacrylate benzyl phosphate |
| CN104844804A (en) * | 2015-03-25 | 2015-08-19 | 沈阳化工大学 | Polymer type phosphorus-nitrogen intumescent flame retardant and preparation method therefor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480319A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Acrylamide copolymer and preparation method and application thereof |
| CN112480677A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Silicon rubber composition and preparation method and application thereof |
| CN113801320A (en) * | 2020-06-01 | 2021-12-17 | 中国石油化工股份有限公司 | Bio-based block polymer, preparation method and application thereof, flame-retardant compound and preparation method thereof |
| CN113801320B (en) * | 2020-06-01 | 2023-11-07 | 中国石油化工股份有限公司 | Bio-based block polymer, preparation method and application thereof, and flame-retardant compound and preparation method thereof |
| CN113512284A (en) * | 2021-04-27 | 2021-10-19 | 骏能化工（龙南）有限公司 | Preparation method of high-flame-retardant polyurethane composite material |
| CN113512284B (en) * | 2021-04-27 | 2022-07-12 | 骏能化工（龙南）有限公司 | Preparation method of high-flame-retardant polyurethane composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108948424B (en) | 2020-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108948424A (en) | A kind of response type phosphonium flame retardant and its preparation method and application | |
| CN109280219B (en) | Efficient furan ring-containing bio-based flame retardant and synthesis method and application thereof | |
| CN106752122B (en) | A kind of nitridation carbon complex, preparation method and application | |
| CN104231266B (en) | Containing large molecule expansion type flame retardant of the structure of hindered amine one-component and its preparation method and application | |
| TWI457353B (en) | Polymers, polymer blends, and flame retardant materials | |
| CN111072973A (en) | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant | |
| CN111234235B (en) | Oligomeric silicon-oxygen phosphate flame retardant and preparation method and application thereof | |
| CN109134544B (en) | A kind of phosphorus nitrile compounds, the composition including the phosphorus nitrile compounds, the fire retardant comprising it and application | |
| CN105175735A (en) | Branched phosphorus-nitrogen type flame retardant and preparation method therefor | |
| CN107652468A (en) | Imidazole sulfonic acid ionic liquid fire retardant, preparation method and application containing DOPO | |
| CN108440598A (en) | A kind of preparation method and applications of sulphur-nitrogen-phosphorus composite fire retardant | |
| CN102492171A (en) | Novel phosphorous siliciferous flame retardant and preparation method thereof | |
| CN109369958A (en) | A kind of preparation method and applications of organic decoration basic zirconium phosphate | |
| CN107056839B (en) | A kind of synthetic method of response type bicyclic phosphate fire retardant | |
| CN102924749A (en) | Ionic liquid-type phosphate fire retardant and preparation method thereof | |
| CN105153228B (en) | A kind of organic phosphor nitrogen combustion inhibitor and the preparation method and application thereof | |
| CN110387042A (en) | Epoxy resin the type fire retardant of topology convergence containing DOPO and preparation method | |
| CN105801867B (en) | A kind of expansion type flame retardant and preparation method thereof based on biomass structure | |
| CN110128702A (en) | Benzene sulphones nitrogen phosphorus sulphur synergistic flame retardant containing double DOPO, preparation method and applications | |
| CN103275118B (en) | Phenyl-phosphonite dipropyl compound and preparation method thereof | |
| CN107129595B (en) | A kind of hyperbranched expandable type fire retardant and preparation method thereof | |
| CN103387673B (en) | Fire retardant and preparation method thereof and purposes | |
| CN110105395A (en) | A kind of pyridine fire retardant and its preparation method and application | |
| CN109180732A (en) | Fire retardant diphenyl time phosphono-N- young laying ducks in cage amine compounds and preparation method thereof | |
| CN104262930B (en) | The polycarbonate compositions of sulfur-bearing and nitrogen organic silicon fibre retardant and preparation method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |