CN1300120C - Synthesizing melamine cyanuric acid by using solution of polyamide resin as reaction medium, and preparation method - Google Patents
Synthesizing melamine cyanuric acid by using solution of polyamide resin as reaction medium, and preparation method Download PDFInfo
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- CN1300120C CN1300120C CNB2005100208886A CN200510020888A CN1300120C CN 1300120 C CN1300120 C CN 1300120C CN B2005100208886 A CNB2005100208886 A CN B2005100208886A CN 200510020888 A CN200510020888 A CN 200510020888A CN 1300120 C CN1300120 C CN 1300120C
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- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000012429 reaction media Substances 0.000 title claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 title 1
- 239000003063 flame retardant Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 3
- 239000000839 emulsion Substances 0.000 claims abstract 4
- 229920000877 Melamine resin Polymers 0.000 claims abstract 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000012456 homogeneous solution Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 18
- 229920002292 Nylon 6 Polymers 0.000 claims description 11
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000299 Nylon 12 Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 23
- 239000000463 material Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- -1 triazine ring compound Chemical class 0.000 description 6
- 102000004895 Lipoproteins Human genes 0.000 description 5
- 108090001030 Lipoproteins Proteins 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000008267 milk Substances 0.000 description 5
- 210000004080 milk Anatomy 0.000 description 5
- 235000013336 milk Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 150000001912 cyanamides Chemical class 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940023462 paste product Drugs 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
聚酰胺树脂溶液为反应介质合成三聚氰胺氰尿酸及其制备方法，其特点是将聚酰胺树脂10-200重量份、浓度为5%～95%的无机酸溶液100～1000重量份，加入带搅拌器、温度计的耐酸反应釜中，于温度20-110℃搅拌5-100分钟使聚酰胺树脂溶解成均相溶液，再依次加入氰尿酸50～110重量份和三聚氰胺50～250重量份，于温度50～120℃搅拌反应10～120分钟，再加入浓度5%～35%的氨水中和至pH＝6～7，使溶解的聚酰胺树脂析出成膜，获得聚酰胺树脂包覆的三聚氰胺氰尿酸的白色乳状液或粘稠膏状物。将上述白色乳状液或粘稠膏状物经过滤、干燥、粉碎后获得0.01～500μm的粉末状产品。该产品作为聚合物的阻燃剂或者与其他阻燃剂一起配合使用。Synthesis of melamine cyanuric acid with polyamide resin solution as the reaction medium and its preparation method, which is characterized in that 100-1000 parts by weight of inorganic acid solution with a concentration of 5% to 95% and 100 to 1000 parts by weight of polyamide resin are added to a stirrer In an acid-resistant reaction kettle with a thermometer, stir at a temperature of 20-110°C for 5-100 minutes to dissolve the polyamide resin into a homogeneous solution, then add 50-110 parts by weight of cyanuric acid and 50-250 parts by weight of melamine in sequence, Stir and react at ~120°C for 10 to 120 minutes, then add ammonia water with a concentration of 5% to 35% to neutralize to pH = 6 to 7, to precipitate the dissolved polyamide resin into a film, and obtain polyamide resin-coated melamine cyanuric acid. White emulsion or viscous paste. The above-mentioned white emulsion or viscous paste is filtered, dried and pulverized to obtain a powder product of 0.01-500 μm. The product is used as a flame retardant for polymers or in combination with other flame retardants.
Description
One, technical field
The present invention relates to a kind of polyamide resin lipoprotein solution is reaction medium production of melamine cyanuric acid and method thereof, belongs to the synthetic field of fire retardant.
Two, background condition
Melamine cyanurate (MCA) is the multi-functional fine chemicals of the beginning of the eighties by Japan's exploitation, its molecular structure is the triazine ring compound that trimeric cyanamide and cyanuric acid are compounded to form by hydrogen bond, its outward appearance is the white crystals micro mist with soapy feeling, nontoxic, tasteless, be insoluble in water and general organic solvent.It is a kind of nitrogen flame retardant of excellent performance, MCA has outstanding advantages such as nitrogen content height, good flame retardation effect, low toxicity, low cigarette, can be used for the fire-retardant of polymkeric substance such as polymeric amide, polyester, polyoxymethylene, urethane, synthetic rubber, Resins, epoxy, the polyamide material that is particularly useful for non-enhancing or filling is fire-retardant.The preparation of flame retardant grade MCA is a raw material with trimeric cyanamide and cyanuric acid generally at present, water is dispersion medium, in temperature 70-120 ℃ of reaction 1～4 hour, head product removed catalyzer after-filtration drying through washing, makes the finished product through superfine grinding again under alkali metal compound or mineral acid catalytic condition.United States Patent (USP) 5202438 has reported that mineral acid catalysis synthesizes the MCA technology, and this technology is carried out building-up reactions under the peracidity of pH≤1, and resultant of reaction is removed inorganic acid catalyst with washing after filtration.This technology is compared with the synthetic MCA technology of the base catalysis of Japanese Patent 56032470 reports, can further reduce water/reactant ratio, and obtain higher productive rate.United States Patent (USP) 4321189 has reported that a kind of reactivity extrudes synthetic MCA route, this technology is compound with nylon 6 respectively with trimeric cyanamide and cyanuric acid, and then two kinds of compound material blend in extruding machine are extruded, trimeric cyanamide and cyanuric acid are reacted at nylon 6 melts, obtained the MCA of crystalline size less than 250 , but because polymer malt viscosity is big, can have a negative impact to reaction conversion ratio, this patented technology yet there are no the report of industrial applications at present.
The consistency of fire retardant and polymer materials and the flame retardant particle dispersion state in resin matrix has material impact to material property.MCA thermostability height directly decomposes distillation and does not have melting process about 400 ℃.MCA is a kind of rigid particles in polymer melt blend recombination process, and it is mobile poor, disperses the phase farmland size of inhomogeneous and disperse phase big, and causing Flame Retardancy to get can not give full play to, and mechanical mechanics property is undesirable.For overcoming above-mentioned shortcoming, need carry out surface modification to the fire retardant powder, Japanese Patent 310716/1993 has been reported polyvinyl alcohol (PVA) process for treating surface of MCA, this technology coats the MCA particle by water-soluble polymers PVA, utilize the lower fusing point of PVA to promote fire retardant homodisperse in resin, but because PVA self decomposition temperature low (180 ℃ thermolysis promptly takes place), modified product is not suitable for the higher engineering plastics of this class processing temperature of polymeric amide.
Three, summary of the invention
The objective of the invention is to provide a kind of polyamide resin lipoprotein solution at the deficiencies in the prior art is reaction medium production of melamine cyanuric acid and preparation method thereof, and it is to integrate the synthetic new technology that reaches surface modification of MCA.Be characterized in polyamide solution, carrying out under the acidic catalyst condition MCA building-up reactions.Mineral acid in the reaction system be catalyzer be again the polyamide resin fatsolvent.Along with reaction is carried out, excessive trimeric cyanamide and inorganic acid reaction generate the trimeric cyanamide inorganic acid salt, acidity is descended, and polyamide resin precipitates gradually separates out the surface filming at MCA, has realized in the fire retardant building-up process compound on the spot with polyamide resin.Reaction finishes the back and adds in the ammoniacal liquor and free acid, regulation system pH to 6-7, make the dissolved polyamide resin separate out film forming, neutralized reaction product inorganic acid ammonium salt and trimeric cyanamide inorganic acid salt itself is present in the flame retardant products as the fire retarding synergist of MCA, play the effect of enhancing condensed phase, so can not need in the reaction product subsequent processes wash.
The present inventor finds, the MCA by present method preparation is owing to have the polyamide resin coating layer of plasticization, flame retardant particle with polyamide-based material melt blending process in flowability and good dispersity, can be implemented in the ultra-fine dispersion in the polymeric matrix.Its Flameproof polyamide material product surface is even, bright and clean, and fire retardant does not have and oozes out and frosting phenomenon.The flame retarding efficiency height of material, mechanical mechanics property is good.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The polyamide resin lipoprotein solution is that the recipe ingredient of the synthetic MCA starting raw material of reaction medium is:
100～200 parts of polyamide resins
100～1000 parts of mass percentage concentration 5%～95% inorganic acid aqueous solutions
50～110 parts of cyanuric acids
50～250 parts of trimeric cyanamides
Wherein polyamide resin is a nylon 6, nylon 66, Ni Long11, nylon 12, nylon 46, at least a in nylon 6/ nylon 66 multipolymers.
Mineral acid is at least a in sulfuric acid and the phosphoric acid.
The polyamide resin lipoprotein solution is the preparation method of the synthetic MCA of reaction medium:
With polyamide resin 10-200 part, mass percentage concentration is 100～1000 parts of 5%～95% inorganic acid solutions, add belt stirrer, in the acid-resistant reacting kettle of thermometer, made polyamide resin dissolve the formation homogeneous phase solution fully in 5～100 minutes in 20～110 ℃ of stirrings of temperature, add 50～250 parts of 50～110 parts of cyanuric acids and trimeric cyanamides more successively, in temperature 50-120 ℃ stirring reaction 10～120 minutes, the ammoniacal liquor that adds concentration 5%～35% again is neutralized to pH=6～7, make the dissolved polyamide resin separate out film forming, obtain white milk sap or the thickness paste of the MCA of polyamide resin coating.
With above-mentioned white milk sap or thickness paste after filtration, dry, pulverize the powdery product that the back obtains 0.01～500 μ m.This product is used as flame retardant of polymer or with other fire retardants.
The present invention has following advantage:
(1) mineral acid catalysis synthetic MCA and polyamide resin are compound on the spot, realize its surface modification.
(2) acid catalyst all changes into flame retardant compositions, can not carry out carrying out washing treatment.
(3) prepared MCA and polyamide resin consistency are good, surperficial plasticization in the melt blending process, and flowability and good dispersity can be realized the ultra-fine dispersion of flame retardant particle.
(4) prepared MCA has higher flame retarding efficiency than conventional MCA to polyamide material, better apparent mass and good mechanical performance.
Four, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment:
1. 25% sulphuric acid soln 500kg is added in the acid-resistant reacting kettle, add Nylon 6 particle 100kg again, stir 20 clocks for 90 ℃, make its dissolving form homogeneous phase solution in temperature.Add cyanuric acid 60kg successively, trimeric cyanamide 60kg, add ammoniacal liquor after 30 minutes at 95 ℃ of stirring reactions of temperature and be neutralized to pH=7, will obtain thickness paste product filter, dry, pulverize the powder-product that makes averageparticle 3 μ m.
2. 30% phosphoric acid solution 1000kg is added in the acid-resistant reacting kettle, add Nylon 66 particle 200kg again, stir 40 clocks for 50 ℃, make its dissolving homogeneous phase solution in temperature.Add cyanuric acid 100kg successively, trimeric cyanamide 110kg adds ammoniacal liquor at 110 ℃ of stirring reactions of temperature and is neutralized to pH=6 after 120 minutes, and white milk sap product filters with obtaining, dry, the powder-product that makes average particle size 10 μ m after pulverizing.
3. in reactor, 10% sulphuric acid soln 200kg and 30% phosphoric acid solution 300kg are added in the acid-resistant reacting kettle, add nylon 6/ nylon 66 copolymer resin particle 180kg again, stirred 50 minutes for 30 ℃, make its dissolving form homogeneous phase solution in temperature.Add cyanuric acid 110kg successively, trimeric cyanamide 250kg adds ammoniacal liquor in 100 ℃ of stirring reactions of temperature and is neutralized to pH=6.5 after 10 minutes, and white milk sap product filters with obtaining, dry, the powder-product that makes average particle size 50 μ m after pulverizing.
4. 95% sulphuric acid soln 200kg is added in the acid-resistant reacting kettle, add Ni Long11 resin particle 100kg again, stir 50 clocks for 50 ℃, make it dissolve the formation homogeneous phase solution fully in temperature.Add cyanuric acid 60kg successively, trimeric cyanamide 70kg, add ammoniacal liquor after 30 minutes at 95 ℃ of stirring reactions of temperature and be neutralized to pH=7, will obtain thickness paste product filter, dry, pulverize the powder-product that makes averageparticle 3 μ m.
5. 80% phosphoric acid solution 400kg is added in the acid-resistant reacting kettle, add nylon 12 resin particle 70kg again, stir 120 clocks for 70 ℃, make it dissolve homogeneous phase solution fully in temperature.Add cyanuric acid 100kg successively, trimeric cyanamide 110kg adds ammoniacal liquor at 110 ℃ of stirring reactions of temperature and is neutralized to pH=6 after 150 minutes, and white milk sap product filters with obtaining, dry, the powder-product that makes average particle size 10 μ m after pulverizing.
Application example
1. gained Nylon 6 coating modification MCA 8kg among the embodiment 1 and nylon 6 92kg adding mixing machine are carried out pre-mixing, compound is added in the Bitruder again and carry out melt blending in temperature 210-260 ℃, this melt blended material granulation is through injection molding, and its Flame Retardancy can be tested can reach the UL941.6-mmV0 rank.
2. with gained Nylon 66 coating modification MCA 7kg among the embodiment 2 and nylon 66 93kg, add mixing machine and carry out pre-mixing, compound is added in the Bitruder again and carry out melt blending in temperature 230-275 ℃, this melt blended material granulation is through injection molding, and its material product flame retardant properties test can reach the UL941.6-mmV0 rank.
3. with 6/ nylon of gained nylon among the embodiment 3,66 copolymer resin coating modification MCA 10kg and corresponding nylon 6/ nylon 66 multipolymer 90kg, oxidation inhibitor 0.1k, add mixing machine and carry out pre-mixing, compound is added in the Bitruder again and carry out melt blending in temperature 220-270 ℃, this melt blended material granulation is through injection molding, and its Flame Retardancy can be tested can reach the UL941.6-mmV0 rank.
4. with gained Ni Long11 resin-coated modified MC A 9kg and Ni Long11 91kg among the embodiment 4, add mixing machine and carry out pre-mixing, compound is added in the Bitruder again and carry out melt blending in temperature 220-250 ℃, this melt blended material granulation is through injection molding, and its material product flame retardant properties test can reach the UL941.6-mmV0 rank.
5. with 12 resin-coated modified MC A 7kg of gained nylon among the embodiment 5 and nylon 12 88kg, add mixing machine and carry out pre-mixing, compound is added in the Bitruder again and carry out melt blending in temperature 220-250 ℃, this melt blended material granulation is through injection molding, and its material product flame retardant properties test can reach the UL941.6-mmV0 rank.
6. with gained Ni Long11 resin-coated modified MC A 20kg and polyoxymethylene 80kg among the embodiment 4, add mixing machine and carry out pre-mixing, compound is added in the Bitruder again and carry out melt blending in temperature 180-200 ℃, this melt blended material granulation is through injection molding, and its material product flame retardant properties test can reach the UL941.6-mmV0 rank.
7. with gained Nylon 66 coating modification MCA 15kg and vibrin 85kg among the embodiment 2, add mixing machine and carry out pre-mixing, compound is added in the Bitruder again and carry out melt blending in temperature 250-280 ℃, this melt blended material granulation is through injection molding, and its material product flame retardant properties test can reach the UL941.6-mmV0 rank.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100208886A CN1300120C (en) | 2005-05-13 | 2005-05-13 | Synthesizing melamine cyanuric acid by using solution of polyamide resin as reaction medium, and preparation method |
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| CNB2005100208886A CN1300120C (en) | 2005-05-13 | 2005-05-13 | Synthesizing melamine cyanuric acid by using solution of polyamide resin as reaction medium, and preparation method |
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| CN1300120C true CN1300120C (en) | 2007-02-14 |
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| CN103073715B (en) * | 2013-01-17 | 2014-12-17 | 湖南工业大学 | Preparation method of composite material for inorganic modified melamine chlorinated isocyanurate flame-retardant nylon 6 |
| CN104530482B (en) * | 2014-12-16 | 2017-06-06 | 清远市普塞呋磷化学有限公司 | A kind of manufacture method of big particle diameter melamine cyanurate |
| CN107903622A (en) * | 2017-11-23 | 2018-04-13 | 宁波七诺新材料科技有限公司 | Flame-retardant modified nylon and preparation method thereof |
| CN109705469A (en) * | 2019-01-08 | 2019-05-03 | 石家庄煜英新材料科技有限公司 | A kind of PP environment friendly halogen-free fireproof master batch production method |
| CN111410840A (en) * | 2020-05-15 | 2020-07-14 | 四川大学 | A kind of halogen-free flame retardant nylon low-dimensional product material and preparation method |
| CN114380758A (en) * | 2021-12-29 | 2022-04-22 | 广东宇星阻燃新材股份有限公司 | A kind of preparation method of pre-dispersed MCA and its application in PA6 and PBT |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4231189A (en) * | 1977-10-27 | 1980-11-04 | Mordecai Hochberg | Plant growing assembly |
| JPH07149738A (en) * | 1992-12-09 | 1995-06-13 | Mitsui Toatsu Chem Inc | Granular melamine cyanurate and method for producing the same |
| JPH07149739A (en) * | 1993-11-26 | 1995-06-13 | Nissan Chem Ind Ltd | Melamine cyanurate granule and its production |
| JPH11292861A (en) * | 1998-04-09 | 1999-10-26 | Mitsubishi Chemical Corp | Melamine cyanurate and method for producing the same |
| CN1150260C (en) * | 1998-12-10 | 2004-05-19 | 索罗蒂亚公司 | Non-halogenated polyamide composition |
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