CN104194044A - Halogen-free phosphorus-containing flame retardant and preparation method thereof - Google Patents
Halogen-free phosphorus-containing flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of high polymer chemical flame retardants, and particularly relates to a halogen-free phosphorus-containing flame retardant and a preparation method thereof. The halogen-free phosphorus-containing flame retardant can be used for preparing flame-retarded nylon, polyester and other engineering plastics and the like with a flame retardant grade of over V-1. The flame retardant is characterized in that the halogen-free phosphorus-containing flame retardant is synthesized through two steps, wherein in the first step, a flame-retarded esterifying liquid is prepared, namely, 10-60 parts of a phosphorus-containing copolymerized flame retardant and 8-55 parts of dihydric alcohol in parts by mass are reacted under certain conditions, so that the flame-retarded esterifying liquid is obtained; in the second step, the halogen-free phosphorus-containing flame retardant is prepared, namely, by the mass of the flame-retarded esterifying liquid, 10-65 parts of the flame-retarded esterifying liquid, 5-65 parts of diamine and 8-55 parts of ethanol are reacted under certain conditions, so that the halogen-free phosphorus-containing flame retardant is obtained. The phosphorus content of the prepared halogen-free phosphorus-containing flame retardant is about 10%, and the halogen-free phosphorus-containing flame retardant has a good flame retardant effect; the flame retardant is less in addition amount and has a small influence on the mechanical properties of products; the flame retardant can withstand a high temperature of 250 DEG C; and the flame retardant can be applied to the fields of nylon, polyester and other engineering plastics with a flame retardant grade of over V-1.
Description
Technical field
The invention belongs to polymer chemistry flame retardant area, relate in particular to a kind of halogen-free phosphorus-containing fire retardant agent and preparation method, can be used for preparing flame retardant rating and reach fire-retardant nylon, polyester and other engineering plastics etc. more than V-1 level.
Background technology
Along with the development of China's synthetic material industry and the continuous expansion of Application Areas, fire retardant has wide market outlook in the every field such as chemical building material, electronic apparatus, communications and transportation, space flight and aviation, household furniture, upholstery, clothing, food, lodging and transportion--basic necessities of life.In addition, the field such as coalfield, oil field, forest extinguishing has also promoted that China is fire-retardant, fire-fighting medium is produced development faster.China's fire retardant has developed into the second largest polymer modification additive that is only second to softening agent.
Fire retardant is pressed effective element classification, can be divided into phosphorus system, chlorine system, bromine system and antimony base, aluminium base, boryl fire retardant etc.Chlorine system and bromide fire retardant, because its burning produces a large amount of toxic gases, serious to environmental hazard, easily cause secondary disaster.The inorganic combustion inhibitors such as antimony base, aluminium base, boryl fire retardant, himself flame retarding efficiency is not high, conventionally need to add a large amount of inorganic combustion inhibitors and just can reach good flame retardant effect, still, the existence of a large amount of inorganic combustion inhibitors will have a strong impact on the mechanical property of material itself.Improving constantly of people's living standard, has determined that fire retardant must be towards environmental protection, efficient future development.
In existing patent, phosphorus flame retardant all carries out modification to phosphoric acid ester and ammonium polyphosphate mostly.Wherein, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (being called for short DOPO) is widely used.Patent CN 103833947 A have announced a kind of preparation method of the response type phosphonium flame retardant for urethane, adopt DOPO and unsaturated polycarboxylic acid and acid anhydrides to form phosphorous-containing monomers derivative, and then with polyvalent alcohol generation esterification, obtain the agent of response type halogen-free phosphorus-containing fire retardant.Patent CN 103866643 A have announced a kind of preparation method of composite flame-retardant agent, adopt the reactions such as triphenylphosphate, tetramethylolmethane, water glass, Precondensed UreaFormaldehyde Resin, ammonium phosphate, make a kind of composite flame-retardant agent.In the existing patent about fire retardant, it is the flame retardant resistance that material brings that fire retardant has mainly been discussed, and fire retardant is discussed less on the impact of the mechanical property of material own and thermal characteristics.
In traditional method, there is deficiency in various degree at present, mainly contain the following aspects: adding of fire retardant obviously declines material mechanical performance and thermal characteristics.Fire retardant, in the time of burning, produces a large amount of harmful flue dust and corrosive gases, and environment is caused to serious pollution.Addition is many, more than just reaching V-1 level.Fire retardant cost is high, technology controlling and process is complicated, is difficult to suitability for industrialized production.Along with the Sustainable development of the mankind and ecotope is advocated in the whole world, International Environmental Protection legislation increasingly strict, has promoted the fire-retardant to efficient, low cigarette, low toxicity of macromolecular material, multi-functional compound future development.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of halogen-free phosphorus-containing fire retardant agent and preparation method, halogen-free phosphorus-containing fire retardant agent flame retarding efficiency that the present invention obtains is high, addition is few,, safety little, high temperature resistant to Mechanical Properties of Products and Effect of Thermal Performance, environmental protection.Preparation method and equipment used are simple, stay in grade, and flexibility of operation is strong.
Solve a kind of halogen-free phosphorus-containing fire retardant agent of above technical problem, it is characterized in that: described halogen-free phosphorus-containing fire retardant agent is by two step synthesis, the first step is the preparation of fire-retardant esterifying liquid, formula is by 10 ~ 60 parts of the phosphorous copoly type fire retardants of mass parts, 8 ~ 55 parts of compositions of dibasic alcohol, the two reacts under certain condition, obtains fire-retardant esterifying liquid; Second step is the preparation of halogen-free phosphorus-containing fire retardant agent, with fire-retardant esterifying liquid Mass Calculation, and 10 ~ 65 parts of fire-retardant esterifying liquids, 5 ~ 65 parts of diamines, 8 ~ 55 parts of ethanol, after reaction, obtain halogen-free phosphorus-containing fire retardant agent under certain condition;
The present invention introduces ignition-proof element phosphorus with halogen-free phosphorus-containing fire retardant agent as matrix fire retardant, uses dibasic alcohol to react with the part active group in halogen-free phosphorus-containing fire retardant agent, makes the fire retardant after modification contain highly active hydroxyl and carboxylic group.Because obtained flame-retardant esterifying liquid acid number is higher, larger on the pH value impact of high molecular polymerization system, therefore with diamine, it is neutralized, obtain pH value and be neutral halogen-free phosphorus-containing fire retardant agent.Regulate reactant ratio, can obtain the product of different structure, for ensureing that the agent of gained halogen-free phosphorus-containing fire retardant has higher phosphorus content, select this proportioning, make the agent of gained halogen-free phosphorus-containing fire retardant there is good flame retardant resistance.
Wherein, described phosphorous copoly type fire retardant is one or more the mixture with following structure:
，
Wherein, R is C
1~ C
7alkyl, phenyl or benzyl, R
＇and R
＂for C
1~ C
15fisher's formula or cyclic alkyl;
Described dibasic alcohol is one or more the mixture having in following formula:
In formula: R is C
2~ C
6open chain alkyl;
Described diamine is one or more the mixture having in following formula:
In formula: R is C
2~ C
10open chain alkyl or phenyl ring.
In the present invention, preferred version is, described halogen-free phosphorus-containing copoly type fire retardant is one or more the mixture in hydroxymethyl phenyl Hypophosporous Acid, 50, hydroxyethyl phenyl Hypophosporous Acid, 50,2-carboxyethyl phenyl Hypophosporous Acid, 50.
Described dibasic alcohol is one or more the mixture in ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol etc.
Described diamine is one or more the mixture in quadrol, propylene diamine, butanediamine, hexanediamine, decamethylene diamine etc.
Described halogen-free phosphorus-containing fire retardant agent general structure is as follows:
Wherein, R
1and R
2for C
1~ C
7alkyl, phenyl or benzyl, R
3~ R
7for C
1~ C
15fisher's formula or cyclic alkyl.
There is the fire retardant phosphorus content of above general structure in 10% left and right, good flame retardation effect.These based flame retardant two ends are active higher hydroxyl, are easy to be copolymerized on macromolecular chain, make resulting materials have permanent fire retardant effect.
The preparation method of the halogen-free phosphorus-containing fire retardant agent in the present invention, is characterized in that: comprise the following steps:
(1) phosphorous copoly type fire retardant, dibasic alcohol are joined in reactor, stir, while being warming up to 80 DEG C, be filled with nitrogen, at 80 ~ 150 DEG C, react 3 ~ 5h, then be warming up to 150 ~ 170 DEG C, reduced vacuum processing; After reaction finishes, stop heating and stir, treating that temperature in the kettle is down to 100 ~ 120 DEG C, discharging, obtains fire-retardant esterifying liquid;
The object of zone heating is to control reaction process, and the object that the first stage is reacted 3 ~ 5h at 80 ~ 150 DEG C is to make the abundant esterification of raw material, and subordinate phase is reacted and reduced vacuum processing at 150 ~ 170 DEG C, and its object is to remove in time the small molecules in system.
(2) fire-retardant esterifying liquid, diamine and ethanol are added in reactor, stir and heat up, in the time that temperature reaches 70 DEG C, pass into nitrogen, under 70 ~ 140 DEG C of conditions, react 3 ~ 5h, reduced vacuum is processed for some time subsequently, reaction finishes, and discharging, obtains halogen-free phosphorus-containing fire retardant agent.
The object that first stage is reacted 3 ~ 5h under 70 ~ 140 DEG C of conditions is that raw material is fully reacted, and subordinate phase is reacted reduced vacuum processing at 70 ~ 140 DEG C, and its object is to remove in time the small molecules in system.The object of logical nitrogen is that protection diamine is not oxidized.
Order of addition(of ingredients) described in preparation method can be: step first adds reactor by dibasic alcohol in (1), is heated to 80 DEG C, then adds gradually phosphorous copoly type fire retardant.
In described step (2), first fire-retardant esterifying liquid and ethanol are added in reactor and stirred, be heated to 70 DEG C, then add gradually diamine.
Reduced vacuum in described step (1) and step (2) is treated to: vacuum tightness is at-0.01 ~-0.096MPa, and the treatment time is 3 ~ 6h.
Reaction end in described step (1) is esterification yield >=99%, produces yield >=85% without cut.; Reaction end in step (2) is that solid content is more than 80%.
The halogen-free phosphorus-containing fire retardant agent that the present invention obtains has following beneficial effect:
(1) phosphorus content is in 10% left and right, and flame retarding efficiency is high;
(2) good flame retardation effect, addition is few, little to Mechanical Properties of Products and Effect of Thermal Performance;
(3) high temperature resistant, under 250 DEG C of conditions, do not decompose;
(4) Halogen, low cigarette, low toxicity, corrosion-free, safety, environmental protection;
(5) technique, equipment are simple, stay in grade, and flexibility of operation is strong etc.;
The fire retardant that the present invention obtains belongs to halogen-free phosphorus-containing fire retardant agent, utilizes phosphorus flame retardant to promote polymkeric substance charing, plays fire retardation in condensed phase, has the advantages such as efficient, low toxicity.The halogen-free phosphorus-containing fire retardant agent that adds the present invention to obtain in polycondensation phase, fire retardant is fixed on nylon macromolecular chain in the mode of copolymerization, in use procedure, does not dissolve, and not dialysis, has permanent fire retardant effect.
Concrete reaction principle is as follows:
A: the preparation of fire-retardant esterifying liquid
B: the preparation of halogen-free phosphorus-containing fire retardant agent
That the halogen-free phosphorus-containing fire retardant agent of preparing in the present invention has is high temperature resistant, to Mechanical Properties of Products and the little feature of Effect of Thermal Performance, solved the technical barrier that existing fire retardant exists, be a kind of novel, environmental protection, fire retardant efficiently.
Brief description of the drawings
Halogen-free phosphorus-containing fire retardant agent TGA test in Fig. 1 the present invention
Fire-retardant nylon DSC test result in Fig. 2 the present invention
Comparison diagram before and after fire-retardant nylon batten burning in Fig. 3 the present invention
The DSC curve of the fire-retardant esterifying liquid of Fig. 4.
Embodiment
Below by example, the invention will be further described.
Embodiment 1:
Get 1.2Kg ethylene glycol and 1.5Kg hydroxymethyl phenyl Hypophosporous Acid, 50 adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 150 DEG C, then Depressor response 3 ~ 6h under 170 DEG C ,-0.01 ~-0.096MPa, esterification yield reaches more than 99%, in the time producing without cut, stopped reaction, is cooled to 100 DEG C, discharging, obtains fire-retardant esterifying liquid.
Fire-retardant esterifying liquid, 0.4Kg propylene diamine and the 1.1kg ethanol of getting 2.2Kg add in reactor, are warming up to 70 DEG C, logical nitrogen, at 100 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.01 ~-0.096MPa subsequently, when solid content is about 80%, cooling discharge, obtains halogen-free phosphorus-containing fire retardant agent.
Embodiment 2:
get 2.1Kg ethylene glycol and 3Kg hydroxyethyl phenyl Hypophosporous Acid, 50 adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 100 DEG C, then Depressor response 3 ~ 6h under 160 DEG C ,-0.02 ~-0.096MPa, esterification yield reaches more than 99%, while generation without cut, stopped reaction, is cooled to 120 DEG C, discharging, obtains fire-retardant esterifying liquid.
Fire-retardant esterifying liquid, 0.4Kg quadrol and the 1.2kg ethanol of getting 2.6Kg add in reactor, are warming up to 70 DEG C, pass into nitrogen, at 140 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa subsequently, when solid content is about 85%, cooling discharge, obtains halogen-free phosphorus-containing fire retardant agent.
Embodiment 3:
get 2.9Kg butyleneglycol and 2-carboxyethyl phenyl Hypophosporous Acid, 50 3.4Kg adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 80 DEG C, then Depressor response 3 ~ 6h under 150 DEG C ,-0.02 ~-0.096MPa, esterification yield reaches more than 99%, in the time producing without cut, stopped reaction, is cooled to 110 DEG C, discharging, obtains fire-retardant esterifying liquid.
Fire-retardant esterifying liquid, 1.1Kg hexanediamine and the 2.4kg ethanol of getting 4.6Kg add in reactor, are warming up to 70 DEG C, pass into nitrogen, at 80 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa subsequently, when solid content is about 83%, cooling discharge, obtains halogen-free phosphorus-containing fire retardant agent.
Embodiment 4:
get 2.5Kg propylene glycol and 2-carboxyethyl phenyl Hypophosporous Acid, 50 3.4Kg adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 120 DEG C, then Depressor response 3 ~ 6h under 155 DEG C ,-0.02 ~-0.096MPa, esterification yield reaches more than 99%, in the time producing without cut, stopped reaction, is cooled to 95 DEG C, discharging, obtains fire-retardant esterifying liquid.
Fire-retardant esterifying liquid, 1.6Kg decamethylene diamine and the 2.6kg ethanol of getting 4.6Kg add in reactor, are warming up to 70 DEG C, pass into nitrogen, at 120 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa subsequently, when solid content is about 82%, cooling discharge, obtains halogen-free phosphorus-containing fire retardant agent.
Embodiment 5:
Get 2.1Kg ethylene glycol, 2-carboxyethyl phenyl Hypophosporous Acid, 50 3.5Kg adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 90 DEG C, then Depressor response 3 ~ 6h under 165 DEG C ,-0.02 ~-0.096MPa, esterification yield reaches more than 99%, in the time producing without cut, stopped reaction, is cooled to 115 DEG C, discharging, obtains fire-retardant esterifying liquid.
Fire-retardant esterifying liquid, 0.7Kg hexanediamine and 0.2Kg quadrol and the 2.2kg ethanol of getting 4.4Kg add in reactor, be warming up to 70 DEG C, pass into nitrogen, at 90 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa subsequently, when solid content is about 88%, cooling discharge, obtains halogen-free phosphorus-containing fire retardant agent.
To gained halogen-free phosphorus-containing fire retardant of the present invention, TGA test is carried out in agent, the results are shown in Figure 1.
From TGA curve, halogen-free phosphorus-containing fire retardant agent, about 260 DEG C of beginning thermal weight losses, reaches maximum at 380 DEG C of left and right rate of decomposition, and after 390 DEG C, decomposition tends to be steady, and final charring rate is about 7%.Therefore, the halogen-free phosphorus-containing fire retardant agent that the present invention makes is difficult for decomposing at high molecular polymerization temperature, has overcome the defect of reactive flame retardant non-refractory, can be used for the fire-retardant of multiple material, as nylon, polyester, and other engineering plastics etc.
Below taking fire-retardant nylon as example, halogen-free phosphorus-containing fire retardant agent that the present invention the makes impact on Flame Retardancy, mechanical property and thermal characteristics is described.
In nylon polymerization process, add respectively the halogen-free phosphorus-containing fire retardant agent that a certain amount of example 1 ~ 5 makes, obtained flame-retardant nylon is carried out to testing vertical flammability according to UL94 standard, the results are shown in Table 1.
Table 1 fire-retardant nylon testing vertical flammability result
Note: flame-retardant standard assessment method: t
1+ t
2+ 20<30(s), be V-0; 30<t
1+ t
2+ 20<60 is V-1; There is drip phenomenon, certainly fall one-level.In example 5, be burning for the first time without drippage without two of drippages, burning for the second time has part drippage.
As shown in Table 1, the fire-retardant nylon limiting oxygen index(LOI) that interpolation embodiment 1 ~ 5 obtained flame-retardant agent makes all, more than 32%, illustrates that obtained flame-retardant nylon has good flame retardant resistance.According to UL94 standard, t
1+ t
2+ 20<30(s), be V-0 level; But produce because having in its combustion processes to melt to drip, therefore flame retardant rating falls one-level to V-1 level.In general, the halogen-free phosphorus-containing fire retardant agent fire-retardant nylon making with this patent, obtained flame-retardant nylon vertical combustion grade is more than V-1 level, has good flame retardant resistance.
Fire-retardant nylon is prepared in the halogen-free phosphorus-containing fire retardant agent making with example 1 ~ 5, and the mechanical property of obtained flame-retardant nylon is in table 2.
Table 2 fire-retardant nylon mechanical property parameters
As shown in Table 2, contrast every mechanical property of pure PA66, the halogen-free phosphorus-containing fire retardant agent fire-retardant nylon making with the present invention, every mechanical property of obtained flame-retardant nylon is all close to pure PA66, the elongation at break of sample segment and flexural strength have even exceeded pure PA66, tensile strength and shock strength are more lower slightly than pure PA66, also close to pure PA66.Prove thus, the halogen-free phosphorus-containing fire retardant agent that the present invention makes is little to nylon Effect on Mechanical Properties, has overcome the existing response type nylon fire retardant defect large to nylon Effect on Mechanical Properties.
The impact of fire retardant on nylon thermal characteristics, mainly discusses by fusing point.At nylon 66 polymerization stages, the halogen-free phosphorus-containing fire retardant agent that adds respectively a certain amount of the present invention to make, obtains the fire-retardant nylon of 13 batches, is numbered 1 ~ 13.Respectively obtained flame-retardant nylon chips is carried out to DSC test, result as shown in Figure 2.
As shown in Figure 2, the fusing point of obtained flame-retardant nylon is all 255 DEG C of left and right, close to 259 DEG C of the theoretical melting temperature (Tm)s of PA66.Illustrate that the response type nylon fire retardant that the present invention makes there is no too large impact to nylon fusing point, traditional response type nylon fire retardant is resolved to the large problem of nylon Effect of Thermal Performance.
The halogen-free phosphorus-containing fire retardant agent fire-retardant nylon making with the present invention, carries out testing vertical flammability to obtained flame-retardant nylon batten, and the state before and after batten burning is shown in Fig. 3.
As shown in Figure 3, after fire-retardant nylon burning, have obvious contraction and become carbon phenomenon, illustrating that the phosphorus in the halogen-free phosphorus-containing fire retardant agent that this patent makes has been brought into play fire retardation, obtained flame-retardant nylon has good flame retardant resistance.
In fire-retardant esterifying liquid preparation technology, to embodiment 1 ~ 2, adopt same materials and same amount, change temperature of reaction, the product structure obtaining is completely different from the structure of the reactive flame retardant described in the present invention, and specific examples is shown in 6 ~ 7.
Embodiment 6:
other proportioning is as embodiment 1, get 1.2Kg ethylene glycol and 1.5Kg hydroxymethyl phenyl Hypophosporous Acid, 50 adds in reactor, esterification 3 ~ 5h at 160 DEG C, then Depressor response 3 ~ 6h under 180 DEG C ,-0.01 ~-0.096MPa, esterification yield reaches more than 99%, in the time being distilled out of without cut, stopped reaction, be cooled to 100 ~ 120 DEG C, discharging, to obtain final product.
Embodiment 7:
other proportioning is as embodiment 2, get 2.1Kg ethylene glycol and 3Kg hydroxyethyl phenyl Hypophosporous Acid, 50 adds in reactor, esterification 3 ~ 5h at 180 DEG C, then Depressor response 3 ~ 6h under 200 DEG C ,-0.01 ~-0.096MPa, esterification yield reaches more than 99%, while being distilled out of without cut, stopped reaction, be cooled to 100 ~ 120 DEG C, discharging, to obtain final product.
In the preparation process of fire-retardant esterifying liquid, temperature is increased to more than 180 DEG C, and halogen-free phosphorus-containing fire retardant agent changes with reacting of dibasic alcohol, obtains after the esterifying liquid described in the present invention, reaction is proceeded, the diverse product of fire retardant structure of gained in final generation and the present invention.Therefore, raising temperature of reaction finally can change the structure of fire retardant.
Because fire-retardant esterifying liquid and diamine all contain two active function groups, in the preparation process of halogen-free phosphorus-containing nylon fire retardant, keep raw material type, temperature of reaction and time constant to embodiment 1 ~ 3, feed change proportioning, the halogen-free phosphorus-containing fire retardant agent that the product structure obtaining makes from this patent is completely different.Specifically see embodiment 8 ~ 10.
Embodiment 8:
Other proportioning is as embodiment 1, fire-retardant esterifying liquid, 0.7Kg quadrol and the 1.4kg ethanol of getting 2.6Kg add in reactor, at 140 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.01 ~-0.096MPa subsequently, when solid content is about 80%, cooling discharge, the product obtaining is designated as halogen-free phosphorus-containing fire retardant agent I.
Embodiment 9:
Other proportioning is as embodiment 2, and fire-retardant esterifying liquid, 0.7Kg propylene diamine and the 1.3kg ethanol of getting 2.2Kg add in reactor, at 100 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.01 ~-0.096MPa subsequently, when solid content is about 80%, cooling discharge, obtains halogen-free phosphorus-containing fire retardant agent I.
Embodiment 10:
Other proportioning is as embodiment 3, and fire-retardant esterifying liquid, 2.1Kg hexanediamine and the 2.9kg ethanol of getting 4.6Kg add in reactor, at 70 DEG C, react 3 ~ 5h, Depressor response 3 ~ 6h under-0.01 ~-0.096MPa subsequently, when solid content is about 80%, cooling discharge, obtains halogen-free phosphorus-containing fire retardant agent I.
Because fire-retardant esterifying liquid is 2-2 functionality system with reacting of diamine, change after its proportioning, product structure changes, and the halogen-free phosphorus-containing fire retardant agent structure that the halogen-free phosphorus-containing fire retardant agent I obtaining makes from this patent is completely different.Compared with the halogen-free phosphorus-containing fire retardant agent making with this patent, the molecular weight of halogen-free phosphorus-containing fire retardant agent I is large, and phosphorus content is low, and flame retardant resistance is relatively poor.The proportioning of the each raw material of this patent is to select ensureing that obtained flame-retardant agent has on the basis of higher phosphorus content, to guarantee that fire retardant has good flame retardant properties.Therefore, reactant ratio is a very important parameter.
The fire-retardant esterifying liquid phosphorus content that this patent the first step makes is about 12%, and the halogen-free phosphorus-containing fire retardant agent phosphorus content making than this patent is high, so consider the fire-retardant esterifying liquid flame retarded polymeric material directly making by this patent the first step.The fire-retardant esterifying liquid that this patent the first step is made carries out DSC test, the results are shown in Figure 4.
As shown in Figure 4, there is strong endothermic peak at 215 DEG C in fire-retardant esterifying liquid, illustrates that, at this temperature, fire-retardant esterifying liquid decomposes rapidly, 240 DEG C of left and right, decomposes and be tending towards complete.Infer thus, fire-retardant esterifying liquid can decompose at high molecular polymerization temperature.Therefore, fire-retardant esterifying liquid can not directly be used as reactive flame retardant flame retarded polymeric material, need to add diamine and ethanol in second step to carry out last preparation.
The halogen-free phosphorus-containing fire retardant agent phosphorus content that the present invention makes, in 10% left and right, has good flame retardant effect; 250 DEG C of high temperature of ability, were difficult for decomposing in the high molecular polymerization stage; According to UL94 standard, more than flame retardant rating can reach V-1 level, good flame retardation effect, is applicable to the fire-retardant of nylon, polyester and other engineering plastics.
Claims (9)
1. a halogen-free phosphorus-containing fire retardant agent, it is characterized in that: described halogen-free phosphorus-containing fire retardant agent is by two step synthesis, the first step is the preparation of fire-retardant esterifying liquid, formula is by 10 ~ 60 parts of the phosphorous copoly type fire retardants of mass parts, 8 ~ 55 parts of compositions of dibasic alcohol, the two reacts under certain condition, obtains fire-retardant esterifying liquid; Second step is the preparation of halogen-free phosphorus-containing fire retardant agent, with fire-retardant esterifying liquid Mass Calculation, and 10 ~ 65 parts of fire-retardant esterifying liquids, 5 ~ 65 parts of diamines, 8 ~ 55 parts of ethanol, after reaction, obtain halogen-free phosphorus-containing fire retardant agent under certain condition;
Wherein, described phosphorous copoly type fire retardant is one or more the mixture with following structure:
or
,
Wherein, R is C
1~ C
7alkyl, phenyl or benzyl, R
＇and R
＂for C
1~ C
15fisher's formula or cyclic alkyl;
Described dibasic alcohol is one or more the mixture having in following formula:
In formula: R is C
2~ C
6open chain alkyl;
Described diamine is one or more the mixture having in following formula:
In formula: R is C
2~ C
10open chain alkyl or phenyl ring.
2. press the halogen-free phosphorus-containing fire retardant agent described in claims 1, it is characterized in that: described phosphorous copoly type fire retardant is one or more the mixture in hydroxymethyl phenyl Hypophosporous Acid, 50, hydroxyethyl phenyl Hypophosporous Acid, 50,2-carboxyethyl phenyl Hypophosporous Acid, 50.
3. press the halogen-free phosphorus-containing fire retardant agent described in claims 1, it is characterized in that: described dibasic alcohol is one or more the mixture in ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol etc.
4. press the halogen-free phosphorus-containing fire retardant agent described in claims 1, it is characterized in that: described diamine is one or more the mixture in quadrol, propylene diamine, butanediamine, hexanediamine, decamethylene diamine etc.
5. a kind of halogen-free phosphorus-containing fire retardant agent according to claim 1, is characterized in that: described halogen-free phosphorus-containing fire retardant agent general structure is as follows:
Wherein, R
1and R
2for C
1~ C
7alkyl, phenyl or benzyl, R
3~ R
7for C
1~ C
15fisher's formula or cyclic alkyl.
6. according to the preparation method of the halogen-free phosphorus-containing fire retardant agent described in claims 1, it is characterized in that: comprise the following steps:
(1) phosphorous copoly type fire retardant, dibasic alcohol are joined in reactor, stir, while being warming up to 80 DEG C, be filled with nitrogen, at 80 ~ 150 DEG C, react 3 ~ 5h, then be warming up to 150 ~ 170 DEG C, reduced vacuum processing; After reaction finishes, stop heating and stir, treating that temperature in the kettle is down to 100 ~ 120 DEG C, discharging, obtains fire-retardant esterifying liquid;
(2) get fire-retardant esterifying liquid, diamine and ethanol and add in reactor, stir and heat up, in the time that temperature reaches 70 DEG C, pass into nitrogen, under 70 ~ 140 DEG C of conditions, react 3 ~ 5h, reduced vacuum is processed for some time subsequently, and reaction finishes, discharging, obtains halogen-free phosphorus-containing fire retardant agent.
7. the preparation method who presses the halogen-free phosphorus-containing fire retardant agent described in claims 6, is characterized in that: described order of addition(of ingredients) is:
Step first adds reactor by dibasic alcohol in (1), is heated to 80 DEG C, then adds gradually phosphorous copoly type fire retardant; After first adding reactor to stir fire-retardant esterifying liquid and ethanol in step (2), be heated to 70 DEG C, then add gradually diamine.
8. the preparation method who presses the halogen-free phosphorus-containing fire retardant agent described in claims 7, is characterized in that:
Reduced vacuum described in step (1) and step (2) is treated to: vacuum tightness is at-0.01 ~ 0.096MPa, and the treatment time is 3 ~ 6h.
9. the preparation method who presses the halogen-free phosphorus-containing fire retardant agent described in claims 7, is characterized in that:
Reaction end in step (1) is esterification yield >=99%, produces yield >=85% without cut; Reaction end in step (2) is that solid content is more than 80%.
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| CN112225902A (en) * | 2020-10-26 | 2021-01-15 | 长春工业大学 | DDP polyphosphate flame retardant and preparation method thereof |
| CN114591623A (en) * | 2022-04-26 | 2022-06-07 | 华润化学材料科技股份有限公司 | High-impact-toughness flame-retardant nylon elastomer material and preparation method thereof |
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| US5750603A (en) * | 1997-05-23 | 1998-05-12 | Solutia Inc. | Polymer-bound non-halogen fire resistant compositions |
| CN101508770B (en) * | 2009-03-17 | 2011-09-14 | 四川东材科技集团股份有限公司 | Method for preparing phosphor system halogen-free flame-proof copolymerization polyester |
| CN101665447A (en) * | 2009-09-22 | 2010-03-10 | 如皋市双马化工有限公司 | Method for synthesizing ethylene stearamide with octadecanoic acid |
| CN101759947B (en) * | 2009-12-29 | 2011-08-03 | 浙江天和树脂有限公司 | Flame-retardant type unsaturated polyester resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112225902A (en) * | 2020-10-26 | 2021-01-15 | 长春工业大学 | DDP polyphosphate flame retardant and preparation method thereof |
| CN114591623A (en) * | 2022-04-26 | 2022-06-07 | 华润化学材料科技股份有限公司 | High-impact-toughness flame-retardant nylon elastomer material and preparation method thereof |
| CN114591623B (en) * | 2022-04-26 | 2023-08-11 | 华润化学材料科技股份有限公司 | Flame-retardant nylon elastomer material with high impact toughness and preparation method thereof |
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