CN104559174A - Preparation method of unenhanced halogen-free flame retardant nylon 66 - Google Patents
Preparation method of unenhanced halogen-free flame retardant nylon 66 Download PDFInfo
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Abstract
The invention relates to a preparation method of an unenhanced halogen-free flame retardant nylon 66, and belongs to the technical field of flame retardant engineering plastics. The method comprises the following steps: synthesizing a halogen-free flame retardant; preparing raw materials according to the following proportions: 65-85 parts by weight of nylon 66 sliced sections, 8-20 parts of self-synthesized halogen-free flame retardant, 1-5 parts of auxiliary flame retardant, 0-2.5 parts of compatilizer, 0.5-2 parts of flexibilizer, 0.5-1.5 parts of silane coupling agent, 1-4 parts of antioxygen; adding the materials into a high-speed mixing machine to uniformly mix; melting and extruding; feeding a mixture into a double-screw extruder for melting, blending and extruding; bracing; water-cooling; and chopping and drying to obtain the flame retardant nylon 66. The prepared flame retardant nylon is high in flame retardance, high in toughness, high in abrasion resistance, high in electric performance, high in heat resistant performance and the like; based on a complex synergistic effect of the self-synthesizing flame retardant and the auxiliary flame retardant, a good and stable effect can be realized, and the preparation method can be widely suitable for the fields of automobiles, mechanical industries, electronic appliances, precise instruments and the like.
Description
Technical field
The present invention relates to a kind of preparation method of non-reinforcing halogen-free flame-proof nylon 66 having, belong to fire-resistant engineering plastics technical field.
Background technology
Along with developing rapidly of electric industry and other special industries, its flame retardant properties of the nylon of non-modified is poor, and its vertical combustion can only reach UL94V-2 level, and oxygen index is about 24, and produces drippage in combustion, belongs to inflammable material.In use very easily initiation fire, especially at electronics field, Yin Nilong and the fire caused is countless, causes damage larger.
The fire retardant kind used in current nylon66 fiber is more, comprising: bromide fire retardant is as decabromodiphenyl oxide, decabromodiphenyl ethane etc.; Phosphorus flame retardant is as red phosphorus; Nitrogenated flame retardant is as trimeric cyanamide, cyanurate (MCA), and solid flame retardant is as antimonous oxide, zinc borate, silicon-dioxide etc.What halogen-free flame-retardant system application was wider is red phosphorus and trimeric cyanamide salt, but red phosphorus band look itself, can only black products be used for, and general only in nylon 6, range of application is narrower.In addition be then trimeric cyanamide salt, mainly trimeric cyanamide urea hydrochlorate and phosphoric acid salt, but its flame retardant effect is not good, and the flame retardant effect extremely unstable formed, general addition is large and can not reach higher flame retardant rating, also can only be applicable to the not high occasion of flame-retardancy requirements.
Summary of the invention
The object of the invention is the preparation method proposing a kind of non-reinforcing halogen-free flame-proof nylon 66 having, to overcome the defect of above-mentioned prior art, by the chemical modification to trimeric cyanamide and derivative thereof, synthesis halogen-free flame retardants, by reaching flame retardant effect with the composite synergistic effect of some auxiliary flame retardants, obtain the high and fire-retardant Nylon 66 that flame retardant effect is stable of flame retardant rating.
The preparation method of the non-reinforcing halogen-free flame-proof nylon 66 having that the present invention proposes, comprises the following steps:
(1) halogen-free flame retardants is synthesized:
Be (1-3) by acyl chloride compound and amine substance according to mol ratio respectively: the ratio of 1 is scattered in toluene, stirring at normal temperature is also heated to 90 DEG C-110 DEG C, back flow reaction 4-8 hour, after filtering, carries out drying in ladder-elevating temperature mode to reflux product, washing product twice, filter, to filtration product dry 3-5 hour at 150 DEG C, obtain white halogen-free antiflaming agent, wherein, described acyl chloride compound is Benzoyl chloride, oxalyl chloride, Acetyl Chloride 98Min., p-phthaloyl chloride, phthalyl chloride, any one in m-phthaloyl chloride or pyromellitic trimethylsilyl chloride, described amine substance is trimeric cyanamide, melamine cyanurate, melamine phosphate, trimeric cyanamide oxalate, trimeric cyanamide hydrochloride, aniline, Ursol D, quadrol, hexanediamine, 4, any one in 4 '-diaminodiphenyl oxide or trolamine, described ladder-elevating temperature mode was: 120 DEG C of dryings 1 hour, was warming up to 150 DEG C of dryings 2 hours, was warming up to 180 DEG C of dryings 2 hours, was warming up to 200 DEG C of dryings 2 hours,
(2) raw material is prepared according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with said ratio and mix, obtain compound;
Wherein, described auxiliary flame retardant is silicon-dioxide, weisspiessglanz, any one in magnalium mixture or zinc borate, described compatilizer is maleic anhydride, epoxy resin or m-pseudoallyl-2, one or more in 2-dimethyl benzoyl isocyanic ester mix mutually with any ratio, described coupling agent is silane resin acceptor kh-550, KH-560, KH-570, described toughner is Phthalates, polyester, between rule 1, 2-polybutadiene or polyamide-based in any one, in described oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 15%-25%, monothioester kind antioxidant 15%-20%, phosphite ester kind antioxidant 55%-70%,
(3) melt extrude: the compound of above-mentioned steps (2) is sent into twin screw extruder carries out that melt blending is extruded, tie rod, water-cooled, pelletizing, drying, obtain non-reinforcing halogen-free flame-proof nylon 66 having, wherein, the each zone temperatures of described expressing technique is respectively: 245 DEG C-260 DEG C, transportation section, melt zone 260 DEG C-280 DEG C, extruding zone 250 DEG C-280 DEG C, exhaust section 240 DEG C-270 DEG C, shearing section 240 DEG C-270 DEG C, described drying temperature is 70 DEG C-115 DEG C.
In above-mentioned preparation method, described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
In above-mentioned preparation method, described monothioester kind antioxidant is Tyox B.
In above-mentioned preparation method, described phosphite ester kind antioxidant is two octadecyl pentaerythritol diphosphites.
The preparation method of the non-reinforcing halogen-free flame-proof nylon 66 having that the present invention proposes, its advantage is: the inventive method is by the chemical modification to trimeric cyanamide and derivative thereof, synthesis halogen-free flame retardants, by reaching flame retardant effect with the composite synergistic effect of some auxiliary flame retardants, obtain the high and fire-retardant Nylon 66 that flame retardant effect is stable of flame retardant rating.Fire-retardant nylon prepared by the inventive method, have that flame retardant resistance is excellent, tough and tensile, wear-resisting, the characteristic such as high electrical property and resistance toheat, and by the composite synergistic effect from synthesis fire retardant and auxiliary flame retardant, fine and stable effect can be played, the fields such as automobile, mechanical industry, electronic apparatus, precision instrument can be widely used in
Embodiment
The preparation method of the non-reinforcing halogen-free flame-proof nylon 66 having that the present invention proposes, comprises the following steps:
(1) halogen-free flame retardants is synthesized:
Be (1-3) by acyl chloride compound and amine substance according to mol ratio respectively: the ratio of 1 is scattered in toluene, stirring at normal temperature is also heated to 90 DEG C-110 DEG C, back flow reaction 4-8 hour, after filtering, carries out drying in ladder-elevating temperature mode to reflux product, washing product twice, filter, to filtration product dry 3-5 hour at 150 DEG C, obtain white halogen-free antiflaming agent, wherein, described acyl chloride compound is Benzoyl chloride, oxalyl chloride, Acetyl Chloride 98Min., p-phthaloyl chloride, phthalyl chloride, any one in m-phthaloyl chloride or pyromellitic trimethylsilyl chloride, described amine substance is trimeric cyanamide, melamine cyanurate, melamine phosphate, trimeric cyanamide oxalate, trimeric cyanamide hydrochloride, aniline, Ursol D, quadrol, hexanediamine, 4, any one in 4 '-diaminodiphenyl oxide or trolamine, described ladder-elevating temperature mode was: 120 DEG C of dryings 1 hour, was warming up to 150 DEG C of dryings 2 hours, was warming up to 180 DEG C of dryings 2 hours, was warming up to 200 DEG C of dryings 2 hours,
(2) raw material is prepared according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with said ratio and mix, obtain compound;
Wherein, described auxiliary flame retardant is silicon-dioxide, weisspiessglanz, any one in magnalium mixture or zinc borate, described compatilizer is maleic anhydride, epoxy resin or m-pseudoallyl-2, one or more in 2-dimethyl benzoyl isocyanic ester mix mutually with any ratio, described coupling agent is silane resin acceptor kh-550, KH-560, KH-570, described toughner is Phthalates, polyester, between rule 1, 2-polybutadiene or polyamide-based in any one, in described oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 15%-25%, monothioester kind antioxidant 15%-20%, phosphite ester kind antioxidant 55%-70%,
(3) melt extrude: the compound of above-mentioned steps (2) is sent into twin screw extruder carries out that melt blending is extruded, tie rod, water-cooled, pelletizing, drying, obtain non-reinforcing halogen-free flame-proof nylon 66 having, wherein, the each zone temperatures of described expressing technique is respectively: 245 DEG C-260 DEG C, transportation section, melt zone 260 DEG C-280 DEG C, extruding zone 250 DEG C-280 DEG C, exhaust section 240 DEG C-270 DEG C, shearing section 240 DEG C-270 DEG C, described drying temperature is 70 DEG C-115 DEG C.
In above-mentioned preparation method, described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
In above-mentioned preparation method, described monothioester kind antioxidant is Tyox B.
In above-mentioned preparation method, described phosphite ester kind antioxidant is two octadecyl pentaerythritol diphosphites.
Below introduce the embodiment of the inventive method:
Embodiment 1
(1) Benzoyl chloride and trimeric cyanamide are scattered in toluene according to the mol ratio of 3:1, stirring at normal temperature post-heating to 108 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 1, productive rate is 90%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 260 DEG C, 275 DEG C, 275 DEG C, 270 DEG C and 265 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 110 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 2
(1) oxalyl chloride and trimeric cyanamide oxalate are scattered in toluene according to the mol ratio of 1.5:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 2, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 255 DEG C, 270 DEG C, 265 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 3
(1) Acetyl Chloride 98Min. and trimeric cyanamide oxalate are scattered in toluene according to the mol ratio of 3:1, stirring at normal temperature post-heating to 97 DEG C, back flow reaction 4 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 3, productive rate is 95%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 268 DEG C, 265 DEG C, 260 DEG C and 250 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 100 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 4
(1) p-phthaloyl chloride and trimeric cyanamide hydrochloride are scattered in toluene according to the mol ratio of 1.5:1, stirring at normal temperature post-heating to 104 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 4, productive rate is 90%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 250 DEG C, 275 DEG C, 275 DEG C, 260 DEG C and 250 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 5
(1) phthalyl chloride and melamine phosphate are scattered in toluene according to the mol ratio of 1.5:1, stirring at normal temperature post-heating to 104 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 5, productive rate is 91%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 250 DEG C, 275 DEG C, 270 DEG C, 260 DEG C and 250 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 80 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 6
(1) m-phthaloyl chloride and melamine cyanurate are scattered in toluene according to the mol ratio of 1.5:1, stirring at normal temperature post-heating to 104 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 6, productive rate is 91%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 250 DEG C, 275 DEG C, 270 DEG C, 260 DEG C and 250 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 80 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 7
(1) pyromellitic trimethylsilyl chloride and trimeric cyanamide are scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 108 DEG C, back flow reaction 8 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 7, productive rate is 85%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 260 DEG C, 280 DEG C, 275 DEG C, 270 DEG C and 265 DEG C, 30min is incubated after arrival design temperature, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, drying, halogen-free flame-proof nylon 66 having, carry out flame retardant resistance to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 8
(1) Benzoyl chloride and trimeric cyanamide are scattered in toluene according to the mol ratio of 3:1, stirring at normal temperature post-heating to 108 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 8, productive rate is 90%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 260 DEG C, 275 DEG C, 270 DEG C, 260 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 110 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 9
(1) oxalyl chloride and trimeric cyanamide oxalate are scattered in toluene according to the mol ratio of 1.5:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 9, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 250 DEG C, 275 DEG C, 270 DEG C, 265 DEG C and 265 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 10
(1) p-phthaloyl chloride and trimeric cyanamide hydrochloride are scattered in toluene according to the mol ratio of 1.5:1, stirring at normal temperature post-heating to 104 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 10, productive rate is 90%.
(2) nylon 6 slice design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 260 DEG C, 280 DEG C, 275 DEG C, 270 DEG C and 265 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 11
(1) oxalyl chloride and quadrol are scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 3 hours, obtain white halogen-free antiflaming agent 11, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 12
(1) oxalyl chloride and 4,4 '-diaminodiphenyl oxide oxalate is scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product washing obtained twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 12, productive rate was 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 13
(1) oxalyl chloride and Ursol D are scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 13, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 14
(1) oxalyl chloride and trolamine are scattered in toluene according to the mol ratio of 1.5:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 3 hours, obtain white halogen-free antiflaming agent 14, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 15
(1) oxalyl chloride and hexanediamine oxalate are scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 15, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 16
(1) oxalyl chloride and quadrol are scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 3 hours, obtain white halogen-free antiflaming agent 16, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 17
(1) oxalyl chloride and 4,4 '-diaminodiphenyl oxide oxalate is scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, drying is carried out in ladder-elevating temperature mode, namely 120 DEG C of dryings 1 hour is warming up to, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product washing obtained twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 17, productive rate was 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 18
(1) oxalyl chloride and Ursol D are scattered in toluene according to the mol ratio of 1:1, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 4 hours, obtain white halogen-free antiflaming agent 18, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 19
(1) oxalyl chloride and aniline are scattered in toluene according to the mol ratio of 1:2, stirring at normal temperature post-heating to 98 DEG C, back flow reaction 5 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 3 hours, obtain white halogen-free antiflaming agent 19, productive rate is 92%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 245 DEG C, 270 DEG C, 270 DEG C, 265 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 105 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 20
(1) Benzoyl chloride and trimeric cyanamide are scattered in toluene according to the mol ratio of 3:1, stirring at normal temperature post-heating to 108 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 20, productive rate is 90%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 260 DEG C, 275 DEG C, 270 DEG C, 260 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 110 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Embodiment 21
(1) Benzoyl chloride and trimeric cyanamide are scattered in toluene according to the mol ratio of 3:1, stirring at normal temperature post-heating to 108 DEG C, back flow reaction 6 hours, after back flow reaction product is filtered, carry out drying in ladder-elevating temperature mode, be namely warming up to 120 DEG C of dryings 1 hour, be warming up to 150 DEG C of dryings 2 hours, be warming up to 180 DEG C of dryings 2 hours, 200 DEG C of dryings 2 hours, the product obtained washing twice, after filtration at 150 DEG C dry 5 hours, obtain white halogen-free antiflaming agent 21, productive rate is 90%.
(2) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(3) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section and shearing section temperature be 260 DEG C, 275 DEG C, 270 DEG C, 260 DEG C and 260 DEG C, 30min is incubated after arrival design temperature, start feeding, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, 110 DEG C of dryings 5 hours, halogen-free flame-proof nylon 66 having, flame retardant resistance is carried out to product, Mechanics Performance Testing is all significantly improved, water absorbability reduces relatively, heat-resistant antifriction strengthens, excellent electrical properties.
Comparative example 1
(1) nylon chips PA66 design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(2) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section, shearing section temperature be 250 DEG C, 270 DEG C, 265 DEG C, 255 DEG C and 250 DEG C, 30min is incubated after arrival design temperature, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, drying, nylon66 fiber, contrast test is carried out to product performance.
Comparative example 2
(1) nylon chips design temperature is 105 DEG C and carries out freeze-day with constant temperature 5 hours, prepare raw material according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with above-mentioned weight part and mix;
(2) preheating is carried out to twin screw extruder, set respectively transportation section, melt zone, extruding zone, exhaust section, shearing section temperature be 250 DEG C, 265 DEG C, 265 DEG C, 260 DEG C and 255 DEG C, 30min is incubated after arrival design temperature, carry out that melt blending is extruded, tie rod, water-cooled, pelletizing, drying, nylon66 fiber, contrast test is carried out to product performance.
The foregoing is only preferred embodiment of the present invention, is only illustrative for invention, and nonrestrictive.Those skilled in the art is understood, and can carry out many changes in the spirit and scope that invention claim limits to it, amendment, even equivalence, but all will fall within the scope of protection of the present invention.
Claims (4)
1. a preparation method for non-reinforcing halogen-free flame-proof nylon 66 having, is characterized in that, this preparation method comprises the following steps:
(1) halogen-free flame retardants is synthesized:
Be (1-3) by acyl chloride compound and amine substance according to mol ratio respectively: the ratio of 1 is scattered in toluene, stirring at normal temperature is also heated to 90 DEG C-110 DEG C, back flow reaction 4-8 hour, after filtering, carries out drying in ladder-elevating temperature mode to reflux product, washing product twice, filter, to filtration product dry 3-5 hour at 150 DEG C, obtain white halogen-free antiflaming agent, wherein, described acyl chloride compound is Benzoyl chloride, oxalyl chloride, Acetyl Chloride 98Min., p-phthaloyl chloride, phthalyl chloride, any one in m-phthaloyl chloride or pyromellitic trimethylsilyl chloride, described amine substance is trimeric cyanamide, melamine cyanurate, melamine phosphate, trimeric cyanamide oxalate, trimeric cyanamide hydrochloride, aniline, Ursol D, quadrol, hexanediamine, 4, any one in 4 '-diaminodiphenyl oxide or trolamine, described ladder-elevating temperature mode was: 120 DEG C of dryings 1 hour, was warming up to 150 DEG C of dryings 2 hours, was warming up to 180 DEG C of dryings 2 hours, was warming up to 200 DEG C of dryings 2 hours,
(2) raw material is prepared according to following proportioning:
Add in high-speed mixer after above-mentioned raw materials is weighed with said ratio and mix, obtain compound;
Wherein, described auxiliary flame retardant is silicon-dioxide, weisspiessglanz, any one in magnalium mixture or zinc borate, described compatilizer is maleic anhydride, epoxy resin or m-pseudoallyl-2, one or more in 2-dimethyl benzoyl isocyanic ester mix mutually with any ratio, described coupling agent is silane resin acceptor kh-550, KH-560, KH-570, described toughner is Phthalates, polyester, between rule 1, 2-polybutadiene or polyamide-based in any one, in described oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 15%-25%, monothioester kind antioxidant 15%-20%, phosphite ester kind antioxidant 55%-70%,
(3) melt extrude: the compound of above-mentioned steps (2) is sent into twin screw extruder carries out that melt blending is extruded, tie rod, water-cooled, pelletizing, drying, obtain non-reinforcing halogen-free flame-proof nylon 66 having, wherein, the each zone temperatures of described expressing technique is respectively: 245 DEG C-260 DEG C, transportation section, melt zone 260 DEG C-280 DEG C, extruding zone 250 DEG C-280 DEG C, exhaust section 240 DEG C-270 DEG C, shearing section 240 DEG C-270 DEG C, described drying temperature is 70 DEG C-115 DEG C.
2. preparation method according to claim 1, is characterized in that, described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
3. preparation method as claimed in claim 1, it is characterized in that, described monothioester kind antioxidant is Tyox B.
4. preparation method as claimed in claim 1, is characterized in that, described phosphite ester kind antioxidant is two octadecyl pentaerythritol diphosphites.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106831627A (en) * | 2016-12-27 | 2017-06-13 | 中国石油天然气股份有限公司 | Amide beta-crystal form nucleating agent and preparation method and application thereof |
| CN109137136A (en) * | 2018-07-23 | 2019-01-04 | 陕西科技大学 | A kind of preparation method and application of the compound fibrid of PET-PA66 |
| CN110128820A (en) * | 2019-04-13 | 2019-08-16 | 上海瀚通汽车零部件有限公司 | A kind of timing chain guide rail and its preparation process |
| CN112064138A (en) * | 2020-08-20 | 2020-12-11 | 神马实业股份有限公司 | Preparation method of halogen-free flame-retardant nylon filament |
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| CN101139462A (en) * | 2007-10-09 | 2008-03-12 | 佛山市顺德区高怡新塑料有限公司 | A kind of carbon fiber reinforced halogen-free flame-retardant nylon 66 and preparation method thereof |
| CN102382465A (en) * | 2011-09-30 | 2012-03-21 | 深圳市科聚新材料有限公司 | Halogen-free flame retarding strengthened PA66 material and preparation method thereof |
| CN103333492A (en) * | 2013-07-22 | 2013-10-02 | 深圳市兴盛迪新材料有限公司 | Halogen-free flame retardant nylon resin composition |
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| CN101139462A (en) * | 2007-10-09 | 2008-03-12 | 佛山市顺德区高怡新塑料有限公司 | A kind of carbon fiber reinforced halogen-free flame-retardant nylon 66 and preparation method thereof |
| CN102382465A (en) * | 2011-09-30 | 2012-03-21 | 深圳市科聚新材料有限公司 | Halogen-free flame retarding strengthened PA66 material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106831627A (en) * | 2016-12-27 | 2017-06-13 | 中国石油天然气股份有限公司 | Amide beta-crystal form nucleating agent and preparation method and application thereof |
| CN106831627B (en) * | 2016-12-27 | 2019-09-03 | 中国石油天然气股份有限公司 | Amide β crystal form nucleating agent, and preparation method and application thereof |
| CN109137136A (en) * | 2018-07-23 | 2019-01-04 | 陕西科技大学 | A kind of preparation method and application of the compound fibrid of PET-PA66 |
| CN110128820A (en) * | 2019-04-13 | 2019-08-16 | 上海瀚通汽车零部件有限公司 | A kind of timing chain guide rail and its preparation process |
| CN112064138A (en) * | 2020-08-20 | 2020-12-11 | 神马实业股份有限公司 | Preparation method of halogen-free flame-retardant nylon filament |
| CN112064138B (en) * | 2020-08-20 | 2022-12-09 | 神马实业股份有限公司 | Preparation method of halogen-free flame-retardant nylon filament |
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