CN104311877A - Reaction type nylon flame retardant and preparation method - Google Patents
Reaction type nylon flame retardant and preparation method Download PDFInfo
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- CN104311877A CN104311877A CN201410432194.2A CN201410432194A CN104311877A CN 104311877 A CN104311877 A CN 104311877A CN 201410432194 A CN201410432194 A CN 201410432194A CN 104311877 A CN104311877 A CN 104311877A
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Abstract
The invention belongs to the field of flame retardants, and especially relates to a reaction type nylon flame retardant and a preparation method. The technical scheme is characterized in that the halonge-free phosphorus-containing nylon flame retardant is synthesized by a two-step process, a first step is preparation of a flame-retardation esterification liquid, the formula comprises 5-52 parts by mass of a halogen-free phosphorus-containing copolymerization type flame retardant and 20-65 parts of a dihydric alcohol, and the flame-retardation esterification liquid is obtained by reacting the above two compositions under a certain condition; and a second step is preparation of the halogen-free phosphorus-containing nylon flame retardant, based on the mass quantity of the flame-retardation esterification liquid, the formula comprises 18-60 parts of the flame-retardation esterification liquid and 5-48 parts of a dibasic acid, and the halogen-free phosphorus-containing nylon flame retardant is obtained by reacting the above two compositions under a certain condition. The obtained flame retardant is resistant to a high temperature of 250 DEG C, satisfies the polymerization temperature of nylon, is polymerized onto a nylon molecular chain in a monomer form in a nylon polymerization process, and has persistent flame retardation effect. The prepared nylon flame retardant has the limit oxygen index of 30% or more, has excellent flame retardation performance, is applicable to produce flame-retardant nylon with the flame retardation performance of UL94V-0 grade or more, and is an efficient environment-friendly nylon flame retardant.
Description
Technical field
The invention belongs to flame retardant area, particularly relate to a kind of response type nylon fire retardant and preparation method, both can be used as reactive flame retardant, and can be used as additive flame retardant again, can be used for the fire-retardant nylon that production flame retardant properties reaches UL94 V-0 level.
Background technology
Nylon (PA) is the general name of the thermoplastic resin containing recurring amide radical group on molecular backbone chain.Nineteen thirty, du pont company released PA first, and PA has developed in the world the class engineering plastics that kind is maximum, output is maximum, consumption is the widest so far.Along with PA is bringing comfortable with simultaneously easily, its inflammableness also brings potential fire hazard hidden danger.Therefore, under keeping the prerequisite of PA mechanical property, need to improve its flame retardant resistance, electrical property and processing characteristics, thermostability etc. further.Worldwide, the research, development and production of fire-retardant PA modification application is more and more received publicity, become the problem that current academia and industry member are jointly paid close attention to and tackled key problems.Successively develop the materials such as flame-retardant PA 66, flame-proof PA 6, fire-retardant reinforced plastic PA66 at present.
The fire-retardant of nylon mainly contains two kinds of approach realizations: the fire retardant of reaction is incorporated in polymerization nylon molecular chain by the method for chemical modification structure by the first; It two is add the way of fire retardant by physics to reach fire-retardant object.The main mode adopting physics to add fire retardant is carried out flame-retardant modified to nylon at present, and it is also relatively less to carry out flame-retardant modified research by chemical means to nylon.Major cause be due to chemical modification may destroy nylon molecular chain structure, reduce fusing point, the mechanical property of nylon is reduced; In addition, easily decompose under the hot environment that common reactive flame retardant synthesizes at nylon, be difficult to be grafted on the molecular chain of nylon.
There is deficiency in various degree in current traditional method, mainly contain the following aspects: fire retardant non-refractory, fast decoupled at nylon polymerization temperature, obtained fire-retardant nylon mechanical property and thermal characteristics obviously decline.Energy consumption is high, environmental pollution is serious, and halogenated flame retardant, when burning, produces a large amount of noxious fume and corrosive gases, causes serious pollution to environment.Fire retardant cost is high, technology controlling and process is complicated, is difficult to suitability for industrialized production.Adding of fire retardant causes other degradation of matrix material, also makes matrix material color be deteriorated, and affects its application.Along with the Sustainable development of the mankind and ecotope is advocated in the whole world, the compound future developments such as it is increasingly strict that International Environmental Protection is made laws, and facilitates the fire-retardant to efficient, low cigarette, low toxicity of macromolecular material, multi-functional.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of response type nylon fire retardant and preparation method, the response type nylon fire retardant in the present invention have flame retarding efficiency high, high temperature resistant, to features such as nylon Effect on Mechanical Properties are little.
Solve a kind of response type nylon fire retardant in the present invention of above technical problem, it is characterized in that: described halogen-free phosphorus-containing nylon fire retardant is by two step synthesis, the first step is the preparation of fire-retardant esterifying liquid, fill a prescription by the halogen-free phosphorus-containing copoly type fire retardant 5 ~ 52 parts of mass parts, dibasic alcohol 20 ~ 65 parts, the two reacts under certain condition, obtains fire-retardant esterifying liquid; Second step is the preparation of halogen-free phosphorus-containing nylon fire retardant, and with fire-retardant esterifying liquid Mass Calculation, fire-retardant esterifying liquid 18 ~ 60 parts, diprotic acid 5 ~ 48 parts, under certain condition after reaction, namely obtain halogen-free phosphorus-containing nylon fire retardant;
Wherein, described halogen-free phosphorus-containing fire retardant agent is one or more the mixture with following structure:
，
In formula: 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 had in following formula:
In formula: R is C
2~ C
6acyclic alkyl;
Described diprotic acid is one or more the mixture had in following formula:
In formula: R is C
1~ C
10acyclic alkyl or phenyl ring.
If directly with halogen-free phosphorus-containing fire retardant agent fire-retardant nylon, in polymerization process, halogen-free phosphorus-containing fire retardant agent molecule chain is difficult to be connected on nylon molecules chain, easily occurs the problems such as the polymerization degree is low, and molecular weight is little, nylon poor mechanical property.The present invention's halogen-free phosphorus-containing fire retardant agent introduces ignition-proof element phosphorus as matrix fire retardant, with the amount of activated radical reaction in dibasic alcohol and halogen-free phosphorus-containing fire retardant agent, modified fire retardant is made to contain highly active oh group, because hydroxyl is easy and carboxyl reaction, flame retardant molecule chain is lengthened, after end carboxyl, to be easilier copolymerized on nylon molecules chain when nylon polymerization, to make nylon have flame retardant resistance.Regulate reactant ratio, the product of different structure can be obtained, for ensureing that gained response type nylon fire retardant has higher phosphorus content, selecting this proportioning, making gained response type nylon fire retardant have good flame retardant resistance.
Preferred version in the present invention can be, and described halogen-free phosphorus-containing fire retardant agent is one or more the mixture in hydroxymethyl phenyl Hypophosporous Acid, 50, hydroxyethyl phenyl Hypophosporous Acid, 50,2-carboxyethyl phenyl Hypophosporous Acid, 50, carboxylic propyl group phenyl Hypophosporous Acid, 50.
Described dibasic alcohol is one or more the mixture in ethylene glycol, propylene glycol, butyleneglycol, pentanediol.
Described diprotic acid is one or more the mixture in propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid etc.
Described response type nylon fire retardant has following general structure:
Wherein, R
1, R
3and R
4for C
1~ C
15fisher's formula or cyclic alkyl; R
2for C
1~ C
7alkyl, phenyl or benzyl.
Have the response type nylon fire retardant of above general structure, in the nylon polymerization stage, flame retardant molecule chain is easy to be copolymerized on nylon molecules chain; To nylon mechanical property and Effect of Thermal Performance little, obtained flame-retardant nylon mechanical property and fusing point are all close to pure nylon; There is phosphorus content high, the advantages such as good flame retardation effect.This based flame retardant overcome current domestic response type nylon fire retardant large to nylon Effect on Mechanical Properties, make the defects such as fusing point sharply reduces, there is higher practical value.
The preparation method of response type nylon fire retardant in the present invention, comprises the following steps:
(1) halogen-free phosphorus-containing fire retardant agent, dibasic alcohol are added in reactor, stir, be 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 process; After reaction terminates, stop heating and stir, treating that temperature in the kettle is down to 100 ~ 120 DEG C, discharging, namely obtain fire-retardant esterifying liquid;
The object of zone heating is to control reaction process, and the object that the first stage reacts 3 ~ 5h at 80 ~ 150 DEG C makes the abundant esterification of raw material, and subordinate phase is reacted and reduced vacuum process at 150 ~ 170 DEG C, its object is to the small molecules in removing system in time.
(2) fire-retardant esterifying liquid, diprotic acid are added in reactor, stir, be warming up to 80 DEG C, be filled with nitrogen, at 80 ~ 150 DEG C, react 3 ~ 5h, be warming up to 150 ~ 170 DEG C subsequently, reduced vacuum process; After reaction terminates, stop heating and stir, treating that temperature in the kettle is down to 100 ~ 120 DEG C, discharging, namely obtain response type nylon fire retardant.
The object that first stage reacts 3 ~ 5h at 80 ~ 150 DEG C is that reactant is fully reacted, and subordinate phase is reacted and reduced vacuum process at 150 ~ 170 DEG C, its object is to the small molecules in removing system in time.
Described step (1) and the reduced vacuum described in step (2) are treated to: vacuum tightness-0.02 ~ 0.096MPa, and the treatment time is 3 ~ 5h.
Described step (1) and the reaction end described in step (2) are produce without cut.
Reaction end in described step (1) is esterification yield >=99%, produces, yield >=85% without cut.
Reaction end in described step (2) is produce without cut, yield >=90%.
The response type nylon fire retardant tool that the present invention obtains has the following advantages:
(1) phosphorus content is about 8%, and flame retarding efficiency is high.
(2) good flame retardation effect, addition is few, little on Mechanical Properties of Products impact.
(3) high temperature resistant, do not decompose under 250 DEG C of conditions.
(4) Halogen, low cigarette, low toxicity, corrosion-free, safety, environmental protection.
(5) simply, stay in grade, flexibility of operation is strong for technique, equipment.
The invention belongs to and form the preparation method that phosphoric acid ester bond obtains ester compound on molecular backbone chain, can be used for the fire-retardant nylon that production flame retardant properties reaches more than UL94 V-0 level.
Reaction principle is as follows:
A: the preparation of fire-retardant esterifying liquid
B: the preparation of response type nylon fire retardant
Response type nylon fire retardant obtained in the present invention has high temperature resistant, does not decompose at nylon polymerization temperature.Addition can make fire-retardant nylon reach V-0 level on a small quantity, and obtained flame-retardant nylon mechanical property and thermal characteristics are all close to pure nylon.There is flame retarding efficiency high, to features such as nylon Effect on Mechanical Properties are little, solve conventional nylon fire retardant non-refractory and to nylon mechanical property, defect that Effect of Thermal Performance is large, be a kind of novel, environmental protection, efficiently nylon fire retardant.
Accompanying drawing explanation
fig. 1 is the response type nylon fire retardant DSC test pattern in the present invention
Fig. 2 is that the response type nylon fire retardant TGA in the present invention schemes
Fig. 3 is comparison diagram before and after the fire-retardant nylon batten burning in the present invention
Fig. 4 is the DSC test pattern of the fire-retardant nylon in the present invention
Embodiment
below in conjunction with embodiment, the present invention will be further described, but protection scope of the present invention, be not limited in this.
embodiment 1:
get 1.8Kg ethylene glycol and 2.5Kg 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 at 170 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 120 DEG C, discharging, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 0.6Kg propanedioic acid of getting 2.2Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, esterification 3h ~ 5h at 150 DEG C, then at 170 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 120 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 2:
get 3.1Kg ethylene glycol and 4.8Kg hydroxyethyl phenyl Hypophosporous Acid, 50 adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 80 DEG C, then at 150 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 100 DEG C, discharging, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 1.6Kg propanedioic acid of getting 6.2Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, esterification 3 ~ 5h at 80 ~ 150 DEG C, then at 150 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 100 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 3:
get 1.8Kg ethylene glycol and 2-carboxyethyl phenyl Hypophosporous Acid, 50 3.1Kg adds in reactor, be warming up to 80 DEG C, pass into nitrogen, abundant stirring, heats up gradually after 2-carboxyethyl phenyl Hypophosporous Acid, 50 all dissolves, esterification 3 ~ 5h at 140 DEG C, then at 160 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 110 DEG C, blowing, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 1.5Kg hexanodioic acid of getting 3.8Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, at 140 degrees Celsius of lower esterification 3 ~ 5h, then at 160 DEG C, Depressor response 3-6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 110 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 4:
get 3.1Kg propylene glycol and 3.5Kg hydroxymethyl phenyl Hypophosporous Acid, 50 adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 130 DEG C, then at 155 DEG C, Depressor response 3 ~ 6 under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 105 DEG C, blowing, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 1.5Kg succinic acid of getting 5.0Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, esterification 3 ~ 5h at 130 DEG C, then at 140 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 105 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 5:
get 3.2Kg propylene glycol and 3.9Kg hydroxyethyl phenyl Hypophosporous Acid, 50 adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 120 DEG C, then at 165 DEG C, Depressor response 3-6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 115 DEG C, blowing, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 2.1Kg hexanodioic acid of getting 5.5Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, esterification 3 ~ 5h at 120 DEG C, then at 170 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 110 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 6:
getting 0.7Kg propylene glycol, 1.1Kg ethylene glycol and 2-carboxyethyl phenyl Hypophosporous Acid, 50 2.8Kg adds in reactor, is warming up to 80 DEG C, passes into nitrogen, abundant stirring, heats up gradually after 2-carboxyethyl phenyl Hypophosporous Acid, 50 all dissolves, esterification 3 ~ 5h at 110 DEG C, then at 150 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 100 DEG C, discharging, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 1.2Kg hexanodioic acid of getting 3.0Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, esterification 3 ~ 5h at 110 DEG C, then at 150 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 100 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 7:
get 3.2Kg butyleneglycol and 3.1Kg hydroxymethyl phenyl Hypophosporous Acid, 50 adds in reactor, pass into nitrogen, esterification 3 ~ 5h at 100 DEG C, then at 170 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, stopped reaction, is cooled to 115 DEG C, discharging, obtain fire-retardant esterifying liquid, cool for subsequent use.
getting the fire-retardant esterifying liquid of 5.5Kg, 0.9Kg succinic acid and 1.0Kg hexanodioic acid adds in reactor, pass into nitrogen, be warming up to 80 DEG C, fully stir, esterification 3 ~ 5h at 100 DEG C, then at 170 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 120 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 8:
getting 2.7Kg butyleneglycol, 1.4Kg hydroxyethyl phenyl Hypophosporous Acid, 50 and 1.7Kg hydroxymethyl phenyl Hypophosporous Acid, 50 adds in reactor, be warming up to 80 DEG C, pass into nitrogen, esterification 3 ~ 5h at 90 DEG C, then at 150 DEG C, Depressor response 3-6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 100 DEG C, discharging, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 1.9Kg hexanodioic acid of getting 5.0Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, esterification 3 ~ 5h at 90 DEG C, then at 155 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 100 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 9:
getting 1.6Kg ethylene glycol, 1.2Kg butyleneglycol and 2-carboxyethyl phenyl Hypophosporous Acid, 50 4.1Kg adds in reactor, is warming up to 80 DEG C, passes into nitrogen, abundant stirring, heats up gradually after 2-carboxyethyl phenyl Hypophosporous Acid, 50 all dissolves, esterification 3 ~ 5h at 115 DEG C, then at 165 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 100 DEG C, discharging, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 2.1Kg hexanodioic acid of getting 5.5Kg add in reactor, pass into nitrogen, be warming up to 80 DEG C, fully stir, esterification 3 ~ 5h at 100 DEG C, then at 160 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 100 DEG C, discharging, obtains response type nylon fire retardant.
embodiment 10:
get 2.2Kg butyleneglycol and 2-carboxyethyl phenyl Hypophosporous Acid, 50 2.6Kg adds in reactor, be warming up to 80 DEG C, pass into nitrogen, abundant stirring, heats up gradually after 2-carboxyethyl phenyl Hypophosporous Acid, 50 all dissolves, esterification 3 ~ 5h at 120 DEG C, then at 150 DEG C, Depressor response 3 ~ 6h under-0.03 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, and stopped reaction, be cooled to 120 DEG C, blowing, obtains fire-retardant esterifying liquid, cools for subsequent use.
fire-retardant esterifying liquid and the 1.3Kg pentanedioic acid of getting 3.9Kg add in reactor, be warming up to 80 DEG C, pass into nitrogen, fully stir, esterification 3 ~ 5h at 120 DEG C, then at 150 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, when producing without cut, stopped reaction, is cooled to 120 DEG C, discharging, obtains response type nylon fire retardant.
in nylon polymerization process, add the fire retardant that a certain amount of above example is obtained respectively, obtained flame-retardant nylon Specifeca tion speeification is in table 1.
The Specifeca tion speeification of table 1 fire-retardant nylon
As shown in Table 1, contrast every mechanical property of pure PA66, the fire-retardant nylon flexural strength of embodiment 1 ~ 6 has exceeded pure PA66, and breaking tenacity, elongation at break and shock strength present reduction in various degree, can be used for fire-retardant nylon engineering plastics; The elongation at break of embodiment 7-10 has exceeded pure PA66, and breaking tenacity and flexural strength, close to pure PA66, can attempt carrying out spinning with this fire-retardant nylon.The limiting oxygen index(LOI) of 10 samples is all more than 30%, and according to UL94 standard, the vertical combustion grade of nylon can reach V-0 level, and flame retardant effect is better.
In general, with the fire retardant nylon that this patent is obtained, flame retardant rating reaches V-0 level, good flame resistance.And this fire retardant is less to nylon Effect on Mechanical Properties, every mechanical property is all close to pure PA66.The problem that conventional flame retardant is large to nylon Effect on Mechanical Properties is resolved.
the response type nylon fire retardant obtained to example 1 carries out TGA analysis, and result as shown in Figure 1.
As shown in Figure 1, TGA curve reflects that the response type nylon fire retardant of example 1 gained is at about 300 DEG C fast degradations, becomes carbon amounts to be about 7%; DSC curve reflects that the maximum decomposition temperature of this fire retardant is about 380 DEG C, good heat resistance.Illustrate that this fire retardant can not decompose at nylon polymerization temperature, be applicable to the fire-retardant of nylon.
at nylon66 fiber polymerization stage, add the response type nylon fire retardant that a certain amount of the present invention obtains respectively, obtain the fire-retardant nylon of 12 batches, be designated as B-1 ~ B-12.Carry out DSC test to obtained flame-retardant nylon chips, result as shown in Figure 2.
From 2, the fusing point of obtained flame-retardant nylon at about 250 DEG C, close to the theoretical melting temperature (Tm) 259 DEG C of PA66.Illustrate that the response type nylon fire retardant that the present invention obtains there is no too large impact to nylon fusing point, traditional response type nylon fire retardant affects large problem to nylon fusing point and is resolved.
the fire retardant nylon obtained 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, have after fire-retardant nylon burning and obviously shrink and become carbon phenomenon, illustrate that the phosphorus in the response type nylon fire retardant that this patent obtains has played fire retardation, obtained flame-retardant nylon has certain flame retardant resistance.
To embodiment 1, adopt same materials and same amount, change temperature of reaction, the product structure obtained is completely different from the response type nylon fire retardant described in this patent, and specific examples is shown in 11.
Embodiment 11:
get 1.8Kg ethylene glycol and 2.5Kg hydroxymethyl phenyl Hypophosporous Acid, 50 adds in reactor, esterification 3 ~ 5h at 80 ~ 180 DEG C, then at 180 ~ 200 DEG C, Depressor response 3 ~ 6h under-0.02 ~-0.096MPa, esterification yield reaches more than 99%, when producing without cut, stopped reaction, be cooled to 100 ~ 120 DEG C, discharging, obtain and the diverse structure of fire-retardant esterifying liquid described in this patent, be designated as fire-retardant esterifying liquid I, cool for subsequent use.
When the structure of fire-retardant esterifying liquid changes, when reacting with diprotic acid, proportioning also can change, and finally causes product structure to change, and products therefrom is designated as fire retardant II.This molecular weight of product is large, and phosphorus content is low, and flame retardant effect is poor.
For the problem of the fire-retardant esterifying liquid fire-retardant nylon that the direct the first step obtains, carry out a series of analysis.The fire-retardant esterifying liquid obtained to the first step of the present invention carries out DSC test, the results are shown in Figure 4.
As shown in Figure 4, there is strong endothermic peak at 232 DEG C in fire-retardant esterifying liquid, illustrates at such a temperature, and fire-retardant esterifying liquid is degraded rapidly, and at about 260 DEG C, degraded is tending towards complete.Infer thus, fire-retardant esterifying liquid can decomposed under the hot conditions of nylon polymerization.Therefore, if directly with fire-retardant esterifying liquid fire-retardant nylon, effect may be undesirable.
For further checking, add a certain amount of embodiment 2 and the obtained fire-retardant esterifying liquid of embodiment 3 at nylon synthesis phase respectively, namely there is no the preparation feedback of second step, do not add diprotic acid, obtain the fire-retardant nylon of two batches, be designated as 1, No. 2 respectively.Several key propertys of obtained flame-retardant nylon are tested, the results are shown in Table 2.
Table 2 fire-retardant nylon important performance characteristic
As shown in Table 2, with the direct fire-retardant nylon of fire-retardant esterifying liquid, there is decline in various degree in the mechanical property of obtained flame-retardant nylon, elongation at break and impact strength decreased obtain especially obvious.The limiting oxygen index(LOI) of obtained flame-retardant nylon is about 26%, and flame retardant rating is V-2 level.Compared with this patent, fire-retardant esterifying liquid is very large to nylon flame retardant resistance and Effect on Mechanical Properties, and flame retardant effect is poor, and the present invention has clear superiority.
The reactant ratio arranged in selection the present invention and processing condition, gained response type nylon fire retardant phosphorus content is high, good flame retardation effect, has excellent flame retardant properties.
The response type nylon fire retardant that the present invention obtains is high temperature resistant, to nylon mechanical property and Effect of Thermal Performance little, be applicable to the fire-retardant of nylon.Be aggregated on nylon molecules chain with monomeric form in nylon polymerization process, there is permanent fire retardant effect; During fire-retardant nylon, limiting oxygen index(LOI) is more than 30%, and have excellent flame retardant properties, can be used for the fire-retardant nylon that production flame retardant resistance reaches more than UL94 V-0 level, is a kind of nylon fire retardant of high-efficiency environment friendly.
Claims (9)
1. a response type nylon fire retardant, it is characterized in that: described halogen-free phosphorus-containing nylon fire retardant is by two step synthesis, the first step is the preparation of fire-retardant esterifying liquid, fill a prescription by the halogen-free phosphorus-containing copoly type fire retardant 5 ~ 52 parts of mass parts, dibasic alcohol 20 ~ 65 parts, the two reacts under certain condition, obtains fire-retardant esterifying liquid; Second step is the preparation of halogen-free phosphorus-containing nylon fire retardant, and with fire-retardant esterifying liquid Mass Calculation, fire-retardant esterifying liquid 18 ~ 60 parts, diprotic acid 5 ~ 48 parts, under certain condition after reaction, namely obtain halogen-free phosphorus-containing nylon fire retardant;
Wherein, described halogen-free phosphorus-containing fire retardant agent is one or more the mixture with following structure:
，
In formula: 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 had in following formula:
In formula: R is C
2~ C
6acyclic alkyl;
Described diprotic acid is one or more the mixture had in following formula:
In formula: R is C
1~ C
10acyclic alkyl or phenyl ring.
2. the response type nylon fire retardant according to claims 1, is characterized in that: described halogen-free phosphorus-containing fire retardant agent is one or more the mixture in hydroxymethyl phenyl Hypophosporous Acid, 50, hydroxyethyl phenyl Hypophosporous Acid, 50,2-carboxyethyl phenyl Hypophosporous Acid, 50, carboxylic propyl group phenyl Hypophosporous Acid, 50.
3. the response type nylon fire retardant according to claims 1, is characterized in that: described dibasic alcohol is one or more the mixture in ethylene glycol, propylene glycol, butyleneglycol, pentanediol.
4. the response type nylon fire retardant according to claims 1, is characterized in that: described diprotic acid is one or more the mixture in propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid etc.
5. the response type nylon fire retardant according to claims 1, is characterized in that: described response type nylon fire retardant has following general structure:
Wherein, R
1, R
3and R
4for C
1~ C
15fisher's formula or cyclic alkyl; R
2for C
1~ C
7alkyl, phenyl or benzyl.
6. the preparation method of the response type nylon fire retardant according to claims 1, is characterized in that: comprise the following steps:
(1) halogen-free phosphorus-containing fire retardant agent, dibasic alcohol are added in reactor, stir, be 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 process; After reaction terminates, stop heating and stir, treating that temperature in the kettle is down to 100 ~ 120 DEG C, discharging, namely obtain fire-retardant esterifying liquid;
(2) fire-retardant esterifying liquid, diprotic acid are added in reactor, stir, be warming up to 80 DEG C, be filled with nitrogen, at 80 ~ 150 DEG C, react 3 ~ 5h, be warming up to 150 ~ 170 DEG C subsequently, reduced vacuum process; After reaction terminates, stop heating and stir, treating that temperature in the kettle is down to 100 ~ 120 DEG C, discharging, namely obtain response type nylon fire retardant.
7. press the synthetic method of the response type nylon fire retardant described in claims 6, it is characterized in that: step (1) and the reduced vacuum described in step (2) are treated to: vacuum tightness-0.02 ~ 0.096MPa, and the treatment time is 3 ~ 6h.
8. press the synthetic method of the response type nylon fire retardant described in claims 6, it is characterized in that: the reaction end in step (1) is esterification yield >=99%, produce without cut, yield >=85%.
9. press the synthetic method of the response type nylon fire retardant described in claims 6, it is characterized in that: the reaction end in step (2) is produce without cut, yield >=90%.
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