CN108070083A - A kind of flame resistant polyamide resin and preparation method thereof - Google Patents
A kind of flame resistant polyamide resin and preparation method thereof Download PDFInfo
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- CN108070083A CN108070083A CN201610975215.4A CN201610975215A CN108070083A CN 108070083 A CN108070083 A CN 108070083A CN 201610975215 A CN201610975215 A CN 201610975215A CN 108070083 A CN108070083 A CN 108070083A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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Abstract
The invention belongs to field of material technology, are related to a kind of flame resistant polyamide resin and preparation method thereof, and the flame resistant polyamide resin, raw materials for production include the component of following parts by weight：20 65 parts of aliphatic dibasic acid, 20 70 parts of aliphatic diamine, brominated 2 20 parts of aliphatic dibasic acid, 0.2 0.6 parts of end-capping reagent, 0.01 0.06 parts of catalyst, 30 160 parts of deionized water.The invention also discloses the preparation methods of above-mentioned material.Compared with prior art, flame resistant polyamide resin prepared by the present invention has the compatibility of halogen fire retardant and polyamide good, so that the homogeneity of product is obviously improved, it adds in a small amount of fire retardant and can reach expected flame retardant property, avoid fire retardant while reducing production cost and added in the influence that multipair properties of product are brought, product mechanical property also be improved significantly.
Description
Technical field
The invention belongs to field of material technology, are related to a kind of flame resistant polyamide resin and preparation method thereof.
Background technology
Polyamide is an earliest kind of engineering plastics development, since nineteen thirty-nine, PA6, PA66, PA11,
The various nylon such as PA12, PA610, PA612, MXD6 are come out one after another, and the annual yield of nylon material is more than 130 × 104T, in work
It occupies an important position in engineering plastics.It is property since it is with characteristics such as nontoxic, light, wear-resisting, corrosion-resistant and good mechanical properties
Excellent, the widely used industrial chemicals of energy, is widely used in the industrial circles such as machinery, automobile, chemical industry, instrument.
Compared with the engineering plastics such as polyester, polyamide is due to containing amido bond, itself has preferable flame retardant property, and oxygen refers to
Number is used between 24-28, but as engineering plastics fire proofings, oxygen index (OI) or relatively low, not up to the 34 of Fv-0 requirements with
On.
Method general at present is to add in have halogen fire retardant during processing modified, and wherein bromide fire retardant is using most
Extensively, it is most common to have decabromodiphenylethane, brominated Polystyrene etc., these methods be all by polyamide, have halogen fire retardant,
Synergistic flame retardant (antimony oxide is in the majority), glass and various auxiliary agents are squeezed out by double screw extruder melt blending.Pass through
This method can be selected flexibly, adjust amount of flame-retardant agent, species etc., obtain the product of required performance.But due to conventionally used
The polarity spectrum of halogen fire retardant and polyamide is larger and polyamide compatibility is not fine, final products mechanics
Performance is affected, and heat resistance is also poor, and it is common to have halogen fire retardant be usually small molecule, decomposition temperature is relatively low, makes
It is also restrained processing temperature must to be blended.In addition, there is halogen fire retardant to also result in system with the poor compatibility of polyamide
Fluidity of molten is deteriorated, and limits the additive amount of the reinforcing materials such as glass, it is relatively low to also result in final products mechanical property.
The content of the invention
A kind of flame resistant polyamide resin is provided it is an object of the invention to overcome the problems of the above-mentioned prior art, it should
Polyamide flame retardant property is good and fluidity of molten increases.
It is a further object to provide a kind of preparation methods of above-mentioned flame resistant polyamide resin.
To achieve the above object, the present invention uses following technical scheme：
A kind of flame resistant polyamide resin, raw materials for production include the component of following parts by weight：
Wherein, the total weight number of the aliphatic dibasic acid, aliphatic diamine and brominated aliphatic dibasic acid is 100
Part.
Preferably, the aliphatic dibasic acid is 30-60 parts；
Preferably, the aliphatic diamine is 30-60 parts；
Preferably, the brominated aliphatic dibasic acid is 5-15 parts；
Preferably, the end-capping reagent is 0.3-0.5 parts；
Preferably, the catalyst is 0.02-0.05 parts；
Preferably, the deionized water is 40-150 parts.
The aliphatic dibasic acid be selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid,
One or more of heneicosanedioic acid, dodecanedioic acid, tridecandioic acid；
Preferably, the aliphatic dibasic acid is adipic acid, decanedioic acid.
The aliphatic diamine is selected from butanediamine, pentanediamine, 2 methyl pentamethylenediamine, hexamethylene diamine, decamethylene diamine, dodecane two
One or more of amine；Preferably, the aliphatic diamine is hexamethylene diamine, decamethylene diamine.
The brominated aliphatic dibasic acid be selected from 2,3- dibromo adipic acids, 2,3- dibromosuccinic acids more than one.
One or more of the end-capping reagent in benzoic acid, acetic acid, propionic acid；Preferably, the end-capping reagent is
Acetic acid.
The catalyst is selected from sodium phosphate, magnesium phosphate, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, phosphorous acid
One or more in zinc, sodium hypophosphite, ortho phosphorous acid magnesium, Lime Hypophosphate or ortho phosphorous acid zinc；Preferably, it is described
Catalyst is sodium hypophosphite.
The present invention also provides a kind of preparation methods of above-mentioned flame resistant polyamide resin, comprise the following steps：
(1) aliphatic dibasic acid, 20-70 parts of aliphatic diamine that parts by weight are 20-65 parts are weighed, 2-20 parts contain
Bromine aliphatic dibasic acid, 0.2-0.6 parts of end-capping reagent, 0.01-0.06 parts of catalyst and 30-160 parts of deionized water adds in
Into autoclave, the residual air that is filled with after being vacuumized in autoclave in the inert gas replacement autoclave,
Retain the inert gas of 30-50kPa after the completion of displacement in autoclave as protection gas；
(2) autoclave is heated to 80-150 DEG C under agitation, when isothermal reaction 1-3 is small, continues afterwards
180-240 DEG C is warming up to, moisture in release autoclave is begun through after pressure reaches 1-3Mpa and maintains 1h makes the height
It presses in reaction kettle in pressure constant state, while when temperature continues to be increased to 220-280 DEG C, then by autoclave pressure release to normal
Pressure；
(3) after autoclave is filled with inert gas, discharging.
Inert gas in the step (1) and (3) is nitrogen；Displacement number described in step (1) is 3-5 times.
Inert gas is filled with reaction kettle in the step (3), until reacting kettle inner pressure reaches 0.5-1.0MPa.
Bromine component is directly connected on the strand of polyamide by resulting product of the present invention by polycondensation reaction, is contained
Bromine binary acid is directly participated in as a part for binary acid in the polymerization process of polyamide, becomes the knot of composition polyamide molecule chain
Structure unit, bromine component, by covalent key connection, compared with prior art, have the following advantages that with binary acid structural unit：
Bromine component is directly connected to the strand of polyamide by polycondensation reaction by products obtained therefrom the firstth, of the present invention
On, it is connected by chemical bond so that the compatibility of bromine atoms and polyamide improves, and avoids the occurrence of phase separation, compatibility not
The problems such as good, improves the performance of final products.
Bromine is directly connected on the strand of polyamide by products obtained therefrom the secondth, of the present invention by polycondensation reaction, bromine
Atom uniformly disperses in polyamide or final processing modified product system, and there is no reunite, disperse non-uniform ask
Topic, so that the homogeneity of product is obviously improved, flame retardant effect also significantly increases, that is, adds in less amount of bromine component, product
Expected flame retardant property is just can reach, reduces the usage amount of fire retardant, reduces production cost, while is avoided fire-retardant
Agent added in the influence of multipair properties of product, and product mechanical property is obviously improved.
3rd, bromine is directly connected on the strand of polyamide by products obtained therefrom of the present invention by polycondensation reaction, with
Being added in processing modified technique general at present has halogen fire retardant to compare, and bromine component passes through altogether with aliphatic dibasic acid structural unit
Valence link connects, and forms homogeneous system so that the crystal property of product, heat resistance improve, heat distortion temperature rise.
4th, bromine is directly connected on the strand of polyamide by products obtained therefrom of the present invention by polycondensation reaction, and two
High molecular polymer is formed by chemical key connection between person, blending is different from and processes common small molecule fire retardant, product
Decomposition temperature is significantly raised, and during the blending and modifying in later stage, processing temperature can also increase, and improve blending and modifying work
The flexibility of skill.
5th, bromine is directly connected on the strand of polyamide by products obtained therefrom of the present invention by polycondensation reaction, bromine
Component is with polyamide by the homogeneous system of formation of chemical bond, and the mobility of product improves, during later stage blending and modifying
The content of the third components such as glass can be greatly increased, so as to improve product mechanical property, reduces production cost.
Specific embodiment
The present invention will be further described by the following examples,
Comparative example
56 parts of adipic acids, 44 parts of hexamethylene diamines, 0.25 part of acetic acid, 0.03 part of sodium hypophosphite, 100 parts of deionized waters are weighed,
And more than component is added in autoclave, it is filled with after being vacuumized in autoclave in nitrogen displacement autoclave
Air 3 times, and retain the nitrogen of 40KPa as protection gas in kettle；
Autoclave is heated to 100 DEG C under stirring condition, when isothermal reaction 1.5 is small, is continuously heating to 220 afterwards
DEG C, 1h is maintained after pressure in kettle reaches 2MPa, starting moisture in release reaction kettle afterwards makes to be in pressure constant state in reaction kettle,
Constant pressure heating 1.5h, when reactor temperature rises to 275 DEG C, by reacting kettle inner pressure pressure release to normal pressure, until without tail gas
Effusion；Nitrogen to pressure is filled with into reaction kettle and reaches 0.7MPa, is discharged up to product.
Embodiment 1
Weigh 52 parts of adipic acids, 42 parts of hexamethylene diamines, 6 parts of dibromo adipic acids, 0.25 part of acetic acid, 0.03 part of sodium hypophosphite,
100 parts of deionized waters, and more than component is added in autoclave, it is filled with nitrogen displacement after being vacuumized in autoclave
Air in autoclave 3 times, and retain the nitrogen of 40KPa as protection gas in kettle；
Autoclave is heated to 100 DEG C under agitation, and isothermal reaction 1.5h is continuously heating to 220 afterwards
DEG C, 1h is maintained after pressure in kettle reaches 2MPa, starting moisture in release reaction kettle afterwards is maintained at reacting kettle inner pressure
2MPa, constant pressure heating 1.5h, when reactor temperature rises to 275 DEG C, by reacting kettle inner pressure pressure release to normal pressure, until not having
Tail gas escapes；Nitrogen to pressure is filled with into reaction kettle and reaches 0.7Mpa, is discharged up to the Flameproof polyamide described in the present embodiment
Resin.
Embodiment 2
Weigh 51 parts of adipic acids, 43 parts of hexamethylene diamines, 6 parts of dibromosuccinic acids, 0.25 part of benzoic acid, 0.03 part of ortho phosphorous acid
Sodium, 100 parts of deionized waters, and more than component is added in autoclave, it is filled with nitrogen after being vacuumized in autoclave
Air in displacement autoclave 3 times, and retain the nitrogen of 45KPa as protection gas in kettle；
Autoclave is heated to 80 DEG C under agitation, and isothermal reaction 3h is continuously heating to 230 DEG C afterwards,
1h is maintained after pressure in kettle reaches 2.5MPa, starting moisture in release reaction kettle afterwards is maintained at reacting kettle inner pressure
2.5MPa, constant pressure heating 1.5h, when reactor temperature rises to 275 DEG C, by reacting kettle inner pressure pressure release to normal pressure, until not having
There is tail gas effusion；Nitrogen to pressure is filled with into reaction kettle and reaches 0.8Mpa, is discharged up to the fire-retardant polyamides described in the present embodiment
Polyimide resin.
Embodiment 3
Weigh 52 parts of decanedioic acid, 45 parts of decamethylene diamines, 3 parts of dibromo adipic acids, 0.2 part of acetic acid, 0.04 part of sodium hypophosphite,
120 parts of deionized waters, and more than component is added in autoclave, it is filled with nitrogen displacement after being vacuumized in autoclave
Air in autoclave 3 times, and retain the nitrogen of 30KPa as protection gas in kettle；
Autoclave is heated to 150 DEG C under agitation, and isothermal reaction 1h is continuously heating to 180 DEG C afterwards,
1h is maintained after pressure in kettle reaches 1.0MPa, starting moisture in release reaction kettle afterwards is maintained at reacting kettle inner pressure
1.0MPa, constant pressure heating 1h, when reactor temperature rises to 220 DEG C, by reacting kettle inner pressure pressure release to normal pressure, until not having
Tail gas escapes；Nitrogen to pressure is filled with into reaction kettle and reaches 1.0Mpa, is discharged up to the Flameproof polyamide described in the present embodiment
Resin.
Embodiment 4
Weigh 55 parts of decanedioic acid, 35 parts of hexamethylene diamines, 6 parts of dibromo adipic acids, 4 parts of dibromosuccinic acids, 0.1 part of acetic acid, 0.1 part
Propionic acid, 0.01 part of sodium hypophosphite, 0.01 part of phosphorous acid magnesium, 150 parts of deionized waters, and more than component is added to reaction under high pressure
In kettle, the air 3 times that is filled with after being vacuumized in autoclave in nitrogen displacement autoclave, and retain 50KPa in kettle
Nitrogen as protection gas；
Autoclave is heated to 120 DEG C under agitation, and isothermal reaction 1.5h is continuously heating to 200 afterwards
DEG C, 1h is maintained after pressure in kettle reaches 1.5MPa, starting moisture in release reaction kettle afterwards is maintained at reacting kettle inner pressure
1.5MPa, constant pressure heating 2h, when reactor temperature rises to 240 DEG C, by reacting kettle inner pressure pressure release to normal pressure, until not having
Tail gas escapes；Nitrogen to pressure is filled with into reaction kettle and reaches 0.6MPa, is discharged up to the Flameproof polyamide described in the present embodiment
Resin.
Embodiment 5
Weigh 64 parts of decanedioic acid, 30 parts of butanediamine, 6 parts of dibromosuccinic acids, 0.3 part of acetic acid, 0.03 part of sodium hypophosphite, 90
Part deionized water, and more than component is added in autoclave, nitrogen displacement height is filled with after being vacuumized in autoclave
Air in pressure reaction kettle 3 times, and retain the nitrogen of 50KPa as protection gas in kettle；
Autoclave is heated to 120 DEG C under agitation, and isothermal reaction 1h is continuously heating to 200 DEG C afterwards,
1h is maintained after pressure in kettle reaches 1.5MPa, starting moisture in release reaction kettle afterwards is maintained at reacting kettle inner pressure
1.5MPa, constant pressure heating 2h, when reactor temperature rises to 240 DEG C, by reacting kettle inner pressure pressure release to normal pressure, until not having
Tail gas escapes；Nitrogen to pressure is filled with into reaction kettle and reaches 0.6MPa, is discharged up to the Flameproof polyamide described in the present embodiment
Resin.
Embodiment 6
Weigh 36 parts of succinic acid, 62 parts of dodecamethylene diamines, 1 part of dibromo adipic acid, 0.3 part of acetic acid, 0.03 part of ortho phosphorous acid
Sodium, 90 parts of deionized waters, and more than component is added in autoclave, being filled with nitrogen after being vacuumized in autoclave puts
The air 3 times in autoclave is changed, and retains the nitrogen of 50KPa as protection gas in kettle；
Autoclave is heated to 120 DEG C under agitation, and isothermal reaction 1h is continuously heating to 200 DEG C afterwards,
1h is maintained after pressure in kettle reaches 1.5MPa, starting moisture in release reaction kettle afterwards is maintained at reacting kettle inner pressure
1.5MPa, constant pressure heating 2h, when reactor temperature rises to 240 DEG C, by reacting kettle inner pressure pressure release to normal pressure, until not having
Tail gas escapes；Nitrogen to pressure is filled with into reaction kettle and reaches 0.6MPa, is discharged up to the Flameproof polyamide described in the present embodiment
Resin.
The performance test results of embodiment 1-6 and comparative example such as table 1.
Table 1
It can be drawn by comparing the polymerization process and test data of comparative example and embodiment 1, the two is except brominated fat
Outside race's binary acid, remaining component, dosage, polymerization technique are essentially identical, and structure of title compound is also essentially identical, so the two has
Similar fusing point, but the oxygen index (OI) of embodiment 1 is significantly raised compared with comparative example, illustrates to increase brominated fat in the course of the polymerization process
Race's dibasic acid component can improve the flame retardant property of product really.By comparing the polymerization process of remaining embodiment and test knot
Fruit also knows that the fusing point of product and the unit component for participating in polymerizeing are closely related, and usual binary acid, the carbon number of diamine are got over
More, fusing point is lower, and vice versa, and if embodiment 3 and embodiment 4 compare, the diamine of embodiment 4 is hexamethylene diamine, compared with embodiment 3
Decamethylene diamine carbon number it is few, thus the fusing point of product also accordingly raises, the brominated aliphatic dibasic acid in raw material, especially former
The bromo element content oxygen index (OI) final to product plays conclusive effect in material.Thus the present invention is by adding in brominated aliphatic
Dibasic acid component improves the oxygen index (OI) of polyamide, so as to improve the flame retardant property of its final products, to later product
Modified production and application have active influence.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using the present invention.
Person skilled in the art obviously can easily make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the invention is not restricted to embodiment here, sheets
Field technology personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be in the present invention
Protection domain within.
Claims (10)
1. a kind of flame resistant polyamide resin, it is characterised in that：Its raw materials for production includes the component of following parts by weight：
Wherein, the total weight number of the aliphatic dibasic acid, aliphatic diamine and brominated aliphatic dibasic acid is 100 parts.
2. flame resistant polyamide resin according to claim 1, it is characterised in that：Preferably, the aliphatic dibasic acid is
30-60 parts；
Preferably, the aliphatic diamine is 30-60 parts；
Preferably, the brominated aliphatic dibasic acid is 5-15 parts；
Preferably, the end-capping reagent is 0.3-0.5 parts；
Preferably, the catalyst is 0.02-0.05 parts；
Preferably, the deionized water is 40-150 parts.
3. flame resistant polyamide resin according to claim 1 or 2, it is characterised in that：The aliphatic dibasic acid is selected from fourth
Diacid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecane two
One or more of acid；
Preferably, the aliphatic dibasic acid is adipic acid, decanedioic acid.
4. flame resistant polyamide resin according to claim 1 or 2, it is characterised in that：The aliphatic diamine is selected from fourth
One or more of diamines, pentanediamine, 2 methyl pentamethylenediamine, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine；
Preferably, the aliphatic diamine is hexamethylene diamine, decamethylene diamine.
5. flame resistant polyamide resin according to claim 1 or 2, it is characterised in that：The brominated aliphatic dibasic acid choosing
From 2,3- dibromo adipic acids, 2,3- dibromosuccinic acids more than one.
6. flame resistant polyamide resin according to claim 1 or 2, it is characterised in that：The end-capping reagent is selected from benzoic acid, second
One or more in acid, propionic acid；
Preferably, the end-capping reagent is acetic acid.
7. flame resistant polyamide resin according to claim 1 or 2, it is characterised in that：The catalyst is selected from sodium phosphate, phosphorus
Sour magnesium, calcium phosphate, sodium phosphite, phosphorous acid magnesium, Arizona bacilli, zinc phosphite, sodium hypophosphite, ortho phosphorous acid magnesium, secondary phosphorous
One or more in sour calcium or ortho phosphorous acid zinc；
Preferably, the catalyst is sodium hypophosphite.
8. a kind of preparation method of flame resistant polyamide resin, it is characterised in that：Comprise the following steps：
(1) aliphatic dibasic acid, 20-70 parts of aliphatic diamine that parts by weight are 20-65 parts, 2-20 parts of brominated fat are weighed
Fat race binary acid, 0.2-0.6 parts of end-capping reagent, 0.01-0.06 parts of catalyst and 30-160 parts of deionized water are added to height
It presses in reaction kettle, the residual air being filled with after being vacuumized in autoclave in the inert gas replacement autoclave, displacement
The inert gas for retaining 30-50kPa in autoclave after finishing is done as protection gas；
(2) autoclave is heated to 80-150 DEG C, when isothermal reaction 1-3 is small under agitation, continues to heat up afterwards
To 180-240 DEG C, moisture in release autoclave is begun through after pressure reaches 1-3Mpa and maintains 1h makes the high pressure anti-
It answers in pressure constant state in kettle, while when temperature continues to be increased to 220-280 DEG C, then by autoclave pressure release to normal pressure；
(3) after autoclave is filled with inert gas, discharging.
9. preparation method according to claim 8, it is characterised in that：Inert gas in the step (1) and (3) is nitrogen
Gas；
Preferably, the displacement number described in step (1) is 3-5 times.
10. preparation method according to claim 8 or claim 9, it is characterised in that：Inert gas is filled with instead in the step (3)
Kettle is answered, until reacting kettle inner pressure reaches 0.5-1.0MPa.
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