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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Abstract
The present invention relates to melamine cyanuric acid synthesized from polyamide resin solution used as reaction media and a preparation method thereof. The present invention is characterized in that 10 to 200 parts of polyamide resin by weight and 100 to 1000 parts of mineral acid solution whose concentration is from 5% to 95% by weight are added into an acid resistant reaction kettle provided with a stirrer and a thermometer the obtained mixture is stirred for 5 to 100 minutes at the temperature of 20 to 110 DEG C, which leads the polyamide resin to be dissolved into homogeneous phase solution; 50 to 110 parts of cyanuric acid by weight and 50 to 250 parts of melamine by weight are orderly added; the mixture is stirred to react for 10 to 120 minutes at the temperature of 50 to 120 DEG C; 5% to 35% of ammonia water whose concentration is from 5% to 35% is added for neutralization until pH is from 6 to 7, which leads the dissolved polyamide resin to be separated and form a film; white emulsion or thick paste of melamine cyanuric acid coated with the polyamide resin can be obtained; the white emulsion or the thick paste is filtered, dried and pulverized, and a powdery product of 0.01 to 500 mum is obtained. The product can be used as a fire retarding agent of polymers, or the product can be matched with other fire retarding agents for use.
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)
1. one kind is reaction medium synthetic melamine cyanurate by the polyamide resin lipoprotein solution, it is characterized in that the recipe ingredient of starting raw material is by weight:
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.
2. melamine cyanurate as claimed in claim 1 is characterized in that mineral acid is at least a in sulfuric acid and the phosphoric acid.
3. the preparation method of melamine cyanurate as claimed in claim 1 or 2 is characterized in that:
(1) with polyamide resin 10-200 weight part, mass percentage concentration is 5%～95% inorganic acid solution 100～1000 weight parts, add belt stirrer, in the acid-resistant reacting kettle of thermometer, stirred 5～100 minutes for 20～110 ℃ in temperature, make polyamide resin be dissolved into homogeneous phase solution, add cyanuric acid 50-110 weight part and trimeric cyanamide 50-250 weight part more successively, in 50～120 ℃ of stirring reactions of temperature 10～120 minutes, the ammoniacal liquor that adds mass percentage concentration 5%～35% again is neutralized to pH=6～7, make the dissolved polyamide resin separate out film forming, obtain white milk sap or thickness paste that polyamide resin coats melamine cyanurate;
(2) with above-mentioned white milk sap or thickness paste after filtration, dry, pulverize the powdery product that the back obtains 0.1-500 μ m.
4. as the purposes of claims 1 described melamine cyanurate, it is characterized in that polyamide resin coats melamine cyanurate and is used as flame retardant of polymer or with other fire retardants.
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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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| CN1696120A CN1696120A (en) | 2005-11-16 |
| CN1300120C true CN1300120C (en) | 2007-02-14 |
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| CN102603662B (en) * | 2011-01-19 | 2014-10-15 | 兆欣化学工业股份有限公司 | Method for recovering caprolactam technological waste liquid to synthesize flame retardant |
| 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 | Halogen-free flame-retardant nylon low-dimensional product material and preparation method thereof |
| CN114380758A (en) * | 2021-12-29 | 2022-04-22 | 广东宇星阻燃新材股份有限公司 | Preparation method of pre-dispersed MCA and application of pre-dispersed MCA in PA6 and PBT |
Citations (5)
| 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 its production |
| 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 its production |
| CN1150260C (en) * | 1998-12-10 | 2004-05-19 | 索罗蒂亚公司 | Non-halogenated polyamide composition |
-
2005
- 2005-05-13 CN CNB2005100208886A patent/CN1300120C/en not_active Expired - Fee Related
Patent Citations (5)
| 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 its production |
| 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 its production |
| CN1150260C (en) * | 1998-12-10 | 2004-05-19 | 索罗蒂亚公司 | Non-halogenated polyamide composition |
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