CN110452528A - Microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 and preparation method - Google Patents
Microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 and preparation method Download PDFInfo
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- CN110452528A CN110452528A CN201910637301.8A CN201910637301A CN110452528A CN 110452528 A CN110452528 A CN 110452528A CN 201910637301 A CN201910637301 A CN 201910637301A CN 110452528 A CN110452528 A CN 110452528A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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Abstract
A kind of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 and preparation method, it is by by with certain flame retardant property, mobility and being not easy the lipophilicity to form a film and red phosphorus powder after the phosphorus-containing carboxylic acid ester size that is insoluble in water thoroughly infiltrates, it is cored greater than 1500 mesh, using the melamine resin with certain flame retardant property as packaging material, washing, suction filtration, forced air drying are obtained after situ aggregation method realizes microcapsule coated.Microcapsule coated infiltration red phosphorus combustion inhibitor is uniformly mixed with nylon 6 slice through batch mixer, by being molded into fire-retardant Nylon 6 finished product batten after twin-screw extruder pelletizing in the same direction, with excellent impact resistant strength, tensile strength and higher yield strain power, and V0 flame retardant rating and flame retardant standard can be reached, the superposition for realizing the composite modified rear various functions characteristic of nylon 6 is promoted.
Description
Technical field
The present invention relates to functional composite material macromolecule synthesising technology fields, specifically relate to a kind of melamine resin
Microcapsule coated infiltrative type red phosphorus combustion inhibitor and its application in nylon 6.
Background technique
Nylon 6 as a kind of important engineering plastics wide range of applications, not only with excellent mechanical property and
Also there is electrical insulation capability wear-resisting, oil resistant, corrosion-resistant, resistance to decomposition and good processing performance to be applied to numerous areas.But by
It in the combustibility of its own, limits it and is requiring the extensive use in higher Material Field now, therefore, solve nylon resistance
Combustion problem has become research hot topic in recent years.
Increasingly with security against fire relevant to life production, the continuous enhancing of environmental consciousness and product flame retardant regulation
Strictly, exploitation halogen-free type fire retardant becomes the research hotspot in present material field.Red phosphorus is a kind of the inorganic of excellent flame retardancy
Fire retardant, compared with other fire retardants, additive amount needed for reaching identical flame retardant property is few at low cost, but common red phosphorus is easy the moisture absorption
Oxidation, and with resin compatible is poor causes nylon while obtaining flame retardant property, corresponding mechanical property has to a certain degree
Reduction, so, become with the consistency problem of substrate and restrict the widely applied development bottleneck of red phosphorus combustion inhibitor.
Summary of the invention
A kind of good with substrate compatibility the purpose of the present invention is inventing, water absorption rate is low, the excellent micro- glue of physical and mechanical property
Capsule coats infiltrative type red phosphorus combustion inhibitor and preparation and its application in nylon 6.
A kind of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, it includes 7 parts of red phosphorus powder, and the red phosphorus powder is average
Mesh number is greater than 1500 mesh.It is 15-85 parts of phosphorus-containing carboxylic acid ester lipophilic and being insoluble in water, anionic phosphorous-containing surfactants 0.1-
0.2 part, 1-2 parts of melamine, 2-3 parts of the formalin of concentration 40%, after nylon 6(is dry) 80-90 parts.
A kind of preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, it is the following steps are included: red phosphorus powder passes through
It crosses after phosphorus-containing carboxylic acid ester size that is lipophilic and being insoluble in water sufficiently infiltrates, is transferred to filtering type centrifugal separator and is centrifugated
Red phosphorus after to infiltration；Then the deionized water high speed dispersion of red phosphorus investment, is slowly added to the phosphorous surface of anionic after infiltrating
Activating agent continues high-speed stirred；After continuing for some time, melamine is added and formaldehyde is dissolved in deionized water at a certain temperature
Manufactured pre-gathering solutions, are slowly added dropwise the concentrated sulfuric acid and adjust pH value, persistently stir certain time and ammonium hydroxide adjusting is added after the reaction was completed
PH value to neutrality, last washed, suction filtration, forced air drying obtains the resistance of melamine resin microcapsule coated infiltrative type red phosphorus
Fire agent.Melamine resin microcapsule coated infiltrative type red phosphorus combustion inhibitor is uniformly mixed with nylon 6 slice through batch mixer, by
Fire-retardant Nylon 6 finished product batten, i.e. microcapsule coated infiltrative type red phosphorus flame-retardant nylon are molded into after twin-screw extruder pelletizing in the same direction
6。
The red phosphorus powder is averaged mesh number greater than 1500 mesh.
Lipophilicity (being insoluble in water) phosphorus-containing carboxylic acid ester size is by phosphoric acid trioctylphosphine ester, tricresyl phosphate butoxyethyl group
Ester, tricresyl phosphate, octyl diphenyl phosphate, tricresyl phosphate diphenyl, tricresyl phosphate (xylyl) ester, phosphorous acid three
One or more of compositions of isopropyl ester.
The red phosphorus powder is sufficiently infiltrated by lipophilic (being insoluble in water) phosphorus-containing carboxylic acid ester size refers to red phosphorus powder
Mass fraction ratio with lipophilic (being insoluble in water) phosphorus-containing carboxylic acid ester size is 1:5 ~ 1:50, persistently stirs 20 ~ 60min.
Red phosphorus is that the red phosphorus quality after infiltration increases by 5 ~ 80% after the infiltration.
The revolving speed of the filtering type centrifugal separator centrifuge separation is 300 ~ 2500r/min.
The deionized water high speed dispersion of red phosphorus investment refers to using tetrafluoro stirring rod after the infiltration, revolving speed is 120 ~
600r/min。
The anionic phosphorous-containing surfactants be by laurel alcohol ether phosphate, Phosphate of Polyoxyethylene Isooctyl Ether,
One or more of compositions of thermally coupled distillation columns, after additive amount and infiltration red phosphorus mass values be (0.002 ~
0.08): 1.
Melamine resin microcapsule coated infiltrative type red phosphorus combustion inhibitor is to be made by the steps:
(1) melamine and formaldehyde are stirred at a temperature of 80 DEG C and is dissolved in deionized water that pre-gathering solutions are made is spare；
(2) mass ratio of red phosphorus and deionized water after infiltrating is 0.05 ~ 0.35, high speed dispersion 20 after putting into deionized water
~ 40min, is then slowly added dropwise anionic phosphorous-containing surfactants, is persistently dispersed to milkiness liquid flooding weak blue fluorescence；
(3) emulsion temp is risen to 85 DEG C, is then slowly added dropwise in pre-gathering solutions 5min made of step (1) and adds；
(4) be slowly added dropwise the concentrated sulfuric acid to PH be 4 or so；
(5) constant temperature persistently stirs 1.5 ~ 2h, and ammonium hydroxide is added after the reaction was completed and adjusts pH value to neutrality；
(6) last washed, suction filtration, forced air drying obtain melamine resin microcapsule coated infiltrative type red phosphorus flame-retardant
Agent.
The microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, is to infiltrate melamine resin microcapsule coated
Type red phosphorus combustion inhibitor with it is dry after nylon 6 and 0.5 part of synergist antimony oxide, antioxidant (BASF (China) has
Limit company, product designation 1098) 0.3 part after mixing, by double screw extruder extruding pelletization, be molded into test through injection molding machine
Batten.
The beneficial effect of this programme is that the flexibility of nylon 6 depends primarily on unformed area in polymer and entirely polymerizeing
Ratio shared by object, specific performance show as notch impact strength, select mesh number to be greater than the red phosphorus powder of 1500 mesh, it is therefore an objective to micro-
When small particle powder is dispersed in 6 inside of nylon, under the premise of the partial size of powder is small and additive amount is little, it will not influence
The flexible motion in the unsetting area of strand, carries out subsequent processing on this basis, can notch impact strength be increased.
Certain fluidity and being not easy is selected to form a film, lipophilic (being insoluble in water) phosphorus-containing carboxylic acid ester size infiltration of lipophilic and flame retardant property
Red phosphorus powder, overcome traditional microcapsules cladding process deionized water infiltration red phosphorus cause finished product red phosphorus combustion inhibitor burning it is slow, resistance
The shortcomings that fuel efficiency fruit lags；Moreover, infiltrating red phosphorus by lipophilic (being insoluble in water) phosphorus-containing carboxylic acid ester size physics, make red phosphorus
Tend to oiliness to be more conducive to surfactant oriented attachment and form fine and close, uniform adsorption layer on red phosphorus surface, it not only can be real
Orientation of the existing clad on red phosphorus surface coats, and reduces the micell weight for being free of red phosphorus, improves the phosphorous effective percentage of coated particle,
Importantly, the water absorption rate of red phosphorus can be greatly lowered and increase substantially microcapsule coated red phosphorus combustion inhibitor and substrate Buddhist nun
The compatibility of dragon 6, to substantially reduce influence of the additive flame retardant to 6 physical property of substrate nylon.Select lipophilic (indissoluble
Yu Shui) the surfactant of phosphorus-containing carboxylic acid ester size and phosphoric acid ester, the two itself have certain flame retardant property, for
The flame retardant property of effective component red phosphorus is also a kind of addition of performance, improves the anti-flammability of covering property red phosphorus to a certain extent
Energy.Meanwhile selecting melamine resin as clad, it is infiltrated with red phosphorus, lipophilicity (being insoluble in water) phosphorus-containing carboxylic acid ester
Agent and anionic phosphorous-containing surfactants form composite flame retardant system, it can be achieved that P-N flame-retardant system flame retardant synergistic effect.One
Kind melamine resin microcapsule coated infiltrative type red phosphorus combustion inhibitor can be red phosphorus combustion inhibitor answering in nylon 6 extensively
With laying a good foundation.
Detailed description of the invention
Fig. 1 is the SEM scanned picture of red phosphorus particle before coating.Fig. 2 is the SEM scanned picture of red phosphorus particle after cladding.
Specific embodiment
Embodiment 1: a kind of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, it is the following steps are included: by phosphoric acid trioctylphosphine
Ester 280g and octyl diphenyl phosphate 120g mixing composition size, selects red phosphorus end to be averaged mesh number as 1500 mesh, weighs red
Phosphor powder 140g and size are stirred in beaker after 0.5h sufficiently infiltrates, and are transferred to filtering type centrifugal separator, revolving speed is adjusted to
500r/min centrifuge separation, the red phosphorus quality after being infiltrated after separation are 230g.Red phosphorus after obtained infiltration is put into
Into deionized water, using tetrafluoro stirring rod high speed dispersion, revolving speed 150r/min；Then be added by laurel alcohol ether phosphate,
The surfactant 11.5g of the ratio composition of Phosphate of Polyoxyethylene Isooctyl Ether 1:1 in mass ratio, continues high-speed stirred into cream
Turbid；40% formalin 40g and melamine 20g are dissolved in 200g deionized water and are configured to pre-gathering solutions；To above-mentioned milkiness
After mixing, pre-gathering solutions are slowly added dropwise in liquid, and 20min is added dropwise.The concentrated sulfuric acid is added dropwise and adjusts pH value between 4 ~ 5, continues
React and ammonium hydroxide is added after 3h adjusts pH value to neutrality, it is last it is washed, filter, that forced air drying obtains melamine resin is micro-
Capsule coats infiltrative type red phosphorus combustion inhibitor, total weight 266g.
Obtained microcapsule coated infiltrative type red phosphorus combustion inhibitor is mixed with nylon 6 slice 1728.4g, synergist three is added
Two antimony 3.5g and antioxidant (BASF China, product designation 1098) 2.1g is aoxidized to mix through batch mixer
It is even, by dry after twin-screw extruder in the same direction (TSE-35 type, eight sections of 235 DEG C ~ 250 DEG C of temperature) pelletizing, finally by injection molding machine
(BT80V type) is molded into fire-retardant Nylon 6 finished product batten, i.e. microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, microcapsule coated leaching
6 batten of profit type red phosphorus flame-retardant nylon is according to ISO527-21-2012 and ISO179-2010 standard cutter size: 80mm × 10mm ×
4mm, using horizontal vertical burning tester (YK-3000) according to the flame retardant rating of UL-94 standard testing batten, oxygen index instrument is surveyed
Combustibility is tried, universal testing machine (ExceedE43 type) tests tensile strength, Charpy impact machine tester (ZBC7000
Type) test notch impact strength (60 ° of Notch angle, depth 2mm, be made by notch sampling machine YJ1251 type).
Embodiment 2: the present embodiment place same as Example 1 repeats no more, the difference is that: a kind of microcapsule coated
Infiltrative type red phosphorus flame-retardant nylon 6, it is the following steps are included: by tricresyl phosphate (xylyl) ester and triisopropyl phosphite mixing group
At size mass ratio 2:1, selects red phosphorus end to be averaged mesh number as 1600 mesh, it is mixed to weigh red phosphorus powder 140g and size 700g
It closes, after stirring 0.5h sufficiently infiltrates, is transferred to filtering type centrifugal separator, revolving speed is adjusted to 900r/min centrifuge separation, weighs infiltration
Red phosphorus quality afterwards is 196g.Then red phosphorus after obtained infiltration is put into deionized water using tetrafluoro stirring rod high speed point
It dissipates, revolving speed 200r/min；Then it is added by Phosphate of Polyoxyethylene Isooctyl Ether, thermally coupled distillation columns by matter
The surfactant 9.8g for measuring the ratio composition than 1:1, continues high-speed stirred into emulsion；Following steps are with embodiment 1, no longer
It repeats.
Last washed, suction filtration, forced air drying obtain melamine resin microcapsule coated infiltrative type red phosphorus flame-retardant
Agent, total weight 227g.
Obtained microcapsule coated infiltrative type red phosphorus combustion inhibitor is mixed with nylon 6 slice 1767.4g, synergist three is added
It aoxidizes two antimony 3.5g and antioxidant (BASF 1098) 2.1g to be uniformly mixed through batch mixer, by twin-screw extruder pelletizing in the same direction
After dry, be finally molded into fire-retardant Nylon 6 finished product batten, i.e. microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, test bars
Flame retardant rating, combustibility, tensile strength and notched impact strength.
Embodiment 3: the present embodiment place same as Example 1 repeats no more, the difference is that: a kind of microcapsule coated
Infiltrative type red phosphorus flame-retardant nylon 6, it is the following steps are included: form leaching by phosphoric acid trioctylphosphine ester and octyl diphenyl phosphate mixing
Moisten agent mass ratio 2:1, selecting the red phosphorus end mesh number that be averaged is that 1800 mesh weigh red phosphorus powder 140g and size 1120g and mix, and is stirred
It mixes after 0.5h sufficiently infiltrates, is transferred to filtering type centrifugal separator, revolving speed is adjusted to 1400r/min centrifuge separation, after weighing infiltration
Red phosphorus quality is 179g.Then red phosphorus after obtained infiltration is put into and uses tetrafluoro stirring rod high speed dispersion in deionized water,
Revolving speed is 260r/min；Then it is added by the ratio of laurel alcohol ether phosphate, thermally coupled distillation columns 1:1 in mass ratio
The surfactant 9g of example composition continues high-speed stirred into emulsion；Following steps are repeated no more with embodiment 1.
Last washed, suction filtration, forced air drying obtain melamine resin microcapsule coated infiltrative type red phosphorus flame-retardant
Agent, total weight 208g.
Obtained microcapsule coated infiltration red phosphorus combustion inhibitor is mixed with nylon 6 slice 1786.4g, three oxygen of synergist is added
Change two antimony 3.5g and antioxidant (BASF 1098) 2.1g to be uniformly mixed through batch mixer, after twin-screw extruder pelletizing in the same direction
It is dry, finally it is molded into fire-retardant Nylon 6 finished product batten, i.e. microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, the resistance of test bars
Fire grade, combustibility, tensile strength and notched impact strength.
Embodiment 4: the present embodiment place same as Example 1 repeats no more, the difference is that: a kind of microcapsule coated
Infiltrative type red phosphorus flame-retardant nylon 6, the following steps are included: it is by tricresyl phosphate, octyl diphenyl phosphate, tricresyl phosphate two
Phenylester mixing composition size mass ratio 1:1:1, select red phosphorus end be averaged mesh number be 1900 mesh weigh red phosphorus powder 140g with
Size 1680g mixing after stirring 0.5h sufficiently infiltrates, is transferred to filtering type centrifugal separator, and revolving speed is adjusted to 2100r/min centrifugation
Separation, the red phosphorus quality after weighing infiltration are 161g.Then red phosphorus after obtained infiltration is put into deionized water using four
Fluorine stirring rod high speed dispersion, revolving speed 500r/min；Then it is added by laurel alcohol ether phosphate, nonylphenol polyoxyethylene ether phosphoric acid
The surfactant 8g of the ratio composition of ester 1:1 in mass ratio, continues high-speed stirred into emulsion；Following steps with embodiment 1,
It repeats no more.
Last washed, suction filtration, forced air drying obtain melamine resin microcapsule coated infiltrative type red phosphorus flame-retardant
Agent, total weight 189g.
Obtained microcapsule coated infiltration red phosphorus combustion inhibitor is mixed with nylon 6 slice 1805.4g, three oxygen of synergist is added
Change two antimony 3.5g and antioxidant (BASF 1098) 2.1g to be uniformly mixed through batch mixer, after twin-screw extruder pelletizing in the same direction
It is dry, finally it is molded into fire-retardant Nylon 6 finished product batten, i.e. microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, the resistance of test bars
Fire grade, combustibility, tensile strength and notched impact strength.
Embodiment 5: the present embodiment place same as Example 3 repeats no more, the difference is that: red phosphorus powder is averaged
Mesh number is 1100 mesh.Red phosphorus quality after infiltration is 149g.Last washed, suction filtration, forced air drying obtain melamino-formaldehyde
Resin microcapsule coats infiltrative type red phosphorus combustion inhibitor, total weight 197g.
Obtained microcapsule coated infiltration red phosphorus combustion inhibitor is mixed with nylon 6 slice 1797.4g, three oxygen of synergist is added
Change two antimony 3.5g and antioxidant (BASF 1098) 2.1g to be uniformly mixed through batch mixer, after twin-screw extruder pelletizing in the same direction
It is dry, finally it is molded into fire-retardant Nylon 6 finished product batten, i.e. microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, the resistance of test bars
Fire grade, combustibility, tensile strength and notched impact strength.
Comparative example 1: a kind of red phosphorus flame-retardant nylon 6, the following steps are included: selection red phosphorus end is averaged, mesh number is 1800 for it
Mesh is mixed according to red phosphorus 140g with nylon 6 slice 1860g, and synergist antimony oxide 3.5g and antioxidant (BASF is added
1098) 2.1g is uniformly mixed through batch mixer, by being molded into fire-retardant Nylon 6 finished product batten after twin-screw extruder pelletizing in the same direction, is surveyed
Flame retardant rating, combustibility, tensile strength and the notched impact strength of testing bar.
Comparative example 2: a kind of melamine resin microcapsule coated red phosphorus combustion inhibitor, it includes the following steps to make
At: it selects red phosphorus end to be averaged mesh number as 1800 mesh, weighs red phosphorus powder 140g and put into deionized water using tetrafluoro stirring rod
Dispersion, revolving speed 200r/min；Then it is added by OP-10 surfactant 7g, persistently stirs into emulsion, 37% formaldehyde is molten
Liquid 100g and melamine 50g, which is dissolved in 200g ionized water, is configured to pre-gathering solutions；After mixing to above-mentioned emulsion, slowly
Pre-gathering solutions are added dropwise, 20min is added dropwise.The concentrated sulfuric acid is added dropwise and adjusts pH value between 4 ~ 5, ammonium hydroxide tune is added after sustained response 3h
PH value is saved to neutrality, last washed, suction filtration, forced air drying obtain melamine resin microcapsule coated type red phosphorus flame-retardant
Agent, last washed, suction filtration, forced air drying obtain melamine resin microcapsule coated red phosphorus combustion inhibitor, and total weight is
165g。
Obtained microcapsule coated red phosphorus combustion inhibitor is mixed with nylon 6 slice 1829.4g, three oxygen of finished product synergist is added
Change two antimony 3.5g and antioxidant (BASF 1098) 2.1g to be uniformly mixed through batch mixer, after twin-screw extruder pelletizing in the same direction
It is dry, finally it is molded into fire-retardant Nylon 6 finished product batten, flame retardant rating, combustibility, tensile strength and the notch punching of test bars
Hit intensity.
Comparative example 3: the present embodiment place same as Example 3 repeats no more, the difference is that: selected infiltration
Agent is trimethyl phosphate (solubility is 500g/L in 25 DEG C of water).
Testing experiment data are as follows:
Claims (10)
1. a kind of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, it is characterized in that it includes 7 parts of red phosphorus powder, the red phosphorus powder
The average mesh number in end is greater than 1500 mesh；15-85 parts of phosphorus-containing carboxylic acid ester lipophilic and being insoluble in water, the phosphorous surface of anionic is living
Property 0.1-0.2 parts of agent, 1-2 parts of melamine, 2-3 parts of the formalin of concentration 40%, it is dry after 6 80-90 parts of nylon.
2. a kind of preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6, it is characterized in that the following steps are included: red phosphorus powder
End by lipophilicity and be insoluble in water phosphorus-containing carboxylic acid ester size sufficiently infiltrate after, be transferred to filtering type centrifugal separator centrifugation point
From red phosphorus after being infiltrated；Then the deionized water high speed dispersion of red phosphorus investment, it is phosphorous to be slowly added to anionic after infiltrating
Surfactant continues high-speed stirred；After continuing for some time, be added melamine and formaldehyde be dissolved at a certain temperature from
Pre-gathering solutions made of sub- water, are slowly added dropwise the concentrated sulfuric acid and adjust pH value, persistently stir certain time and ammonium hydroxide is added after the reaction was completed
PH value is adjusted to neutrality, it is last it is washed, filter, that forced air drying obtains melamine resin microcapsule coated infiltrative type is red
Phosphorus fire retardant；Melamine resin microcapsule coated infiltrative type red phosphorus combustion inhibitor mixes with nylon 6 slice through batch mixer
It is even, by being molded into fire-retardant Nylon 6 finished product batten, i.e. microcapsule coated infiltrative type red phosphorus flame-retardant after twin-screw extruder pelletizing in the same direction
Nylon 6.
3. the preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, characterized in that described
It is lipophilic and to be insoluble in the phosphorus-containing carboxylic acid ester size of water be by phosphoric acid trioctylphosphine ester, three butoxy ethyl ester of phosphoric acid, tricresyl phosphate
Toluene ester, octyl diphenyl phosphate, tricresyl phosphate diphenyl, tricresyl phosphate (xylyl) ester, triisopropyl phosphite
One or more composition.
4. the preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, characterized in that described
Red phosphorus powder by it is lipophilic and be insoluble in water phosphorus-containing carboxylic acid ester size sufficiently infiltrate refer to red phosphorus powder and lipophilicity and
The mass fraction ratio for being insoluble in the phosphorus-containing carboxylic acid ester size of water is 1:5 ~ 1:50, persistently stirs 20 ~ 60min.
5. the preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, characterized in that described
Red phosphorus is that the red phosphorus quality after infiltration increases by 5 ~ 80% after infiltration.
6. the preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, characterized in that described
The revolving speed of filtering type centrifugal separator centrifuge separation is 300 ~ 2500r/min.
7. the preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, characterized in that described
The deionized water high speed dispersion of red phosphorus investment refers to that, using tetrafluoro stirring rod, revolving speed is 120 ~ 600r/min after infiltration.
8. the preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, characterized in that described
Anionic phosphorous-containing surfactants are by laurel alcohol ether phosphate, Phosphate of Polyoxyethylene Isooctyl Ether, polyoxyethylene nonyl phenyl second
One or more of compositions of alkene ether phosphate, additive amount are (0.002 ~ 0.08) with red phosphorus mass values after infiltration: 1.
9. the preparation method of microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, it is characterized in that melamine
Amine-formaldehyde resins microcapsule coated infiltrative type red phosphorus combustion inhibitor is to be made by the steps:
(1) melamine and formaldehyde are stirred at a temperature of 80 DEG C and is dissolved in deionized water that pre-gathering solutions are made is spare；
(2) mass ratio of red phosphorus and deionized water after infiltrating is 0.05 ~ 0.35, high speed dispersion 20 after putting into deionized water
~ 40min, is then slowly added dropwise anionic phosphorous-containing surfactants, is persistently dispersed to milkiness liquid flooding weak blue fluorescence；
(3) emulsion temp is risen to 85 DEG C, is then slowly added dropwise in pre-gathering solutions 5min made of step (1) and adds；
(4) be slowly added dropwise the concentrated sulfuric acid to PH be 4 or so；
(5) constant temperature persistently stirs 1.5 ~ 2h, and ammonium hydroxide is added after the reaction was completed and adjusts pH value to neutrality；
(6) last washed, suction filtration, forced air drying obtain melamine resin microcapsule coated infiltrative type red phosphorus flame-retardant
Agent.
10. the preparation method of capsule cladding infiltrative type red phosphorus flame-retardant nylon 6 according to claim 2, characterized in that described micro-
Capsule coat infiltrative type red phosphorus flame-retardant nylon 6, be by melamine resin microcapsule coated infiltrative type red phosphorus combustion inhibitor with
0.5 part of nylon 6 and synergist, 0.3 part of antioxidant after drying after mixing, by double screw extruder extruding pelletization,
Test bars are molded into through injection molding machine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646366A (en) * | 2020-12-22 | 2021-04-13 | 江苏集萃先进高分子材料研究所有限公司 | Halogen-free environment-friendly flame-retardant master batch of long glass fiber reinforced nylon composite material and preparation method thereof |
| CN113214542A (en) * | 2021-05-18 | 2021-08-06 | 湖南娄底华星锑业有限公司 | Composite antimony trioxide flame retardant and preparation method thereof |
| CN116462930A (en) * | 2023-04-06 | 2023-07-21 | 青岛中新华美塑料有限公司 | Flame-retardant ABS alloy material and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698215A (en) * | 1985-03-19 | 1987-10-06 | Saffa S.P.A. | Stabilized red phosphorus for use as flame-retardant, in particular for compositions on the basis of polymers |
| US20060183835A1 (en) * | 2004-08-12 | 2006-08-17 | Clariant Gmbh | Flame-retardant polymers with glow-wire resistance |
| CN1940014A (en) * | 2006-09-29 | 2007-04-04 | 公安部四川消防研究所 | Whiteness microcapsule red phosphorus and its production |
| CN101503568A (en) * | 2008-02-04 | 2009-08-12 | 金发科技股份有限公司 | Red phosphorus flame-retardant enhanced thermoplastic polyamide composition |
| CN102775814A (en) * | 2012-08-10 | 2012-11-14 | 四川省精细化工研究设计院 | Method for preparing micro-encapsulation red phosphorus |
| CN103980542A (en) * | 2014-05-30 | 2014-08-13 | 王万庆 | Method for preparing dust-free microencapsulated red phosphorus flame retardant |
| CN104017354A (en) * | 2014-06-09 | 2014-09-03 | 温州科力塑业有限公司 | Halogen-free red phosphorus flame retardant nylon with high toughness and preparation method of nylon |
| CN104059388A (en) * | 2014-06-27 | 2014-09-24 | 南京化工职业技术学院 | Double-coated microencapsulated red phosphorus and preparation method thereof |
| CN105295101A (en) * | 2015-12-01 | 2016-02-03 | 中国科学技术大学苏州研究院 | Microencapsulated red phosphorus fire retardant and preparation method and application thereof |
| CN106009045A (en) * | 2016-07-01 | 2016-10-12 | 中国科学院宁波材料技术与工程研究所 | Microencapsulated red phosphorus, and preparation method and application thereof |
| CN109971039A (en) * | 2019-04-09 | 2019-07-05 | 东北林业大学 | A kind of preparation method of modified melamine-formaldehyde resin encapsulated red phosphorus |
-
2019
- 2019-07-15 CN CN201910637301.8A patent/CN110452528B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698215A (en) * | 1985-03-19 | 1987-10-06 | Saffa S.P.A. | Stabilized red phosphorus for use as flame-retardant, in particular for compositions on the basis of polymers |
| US20060183835A1 (en) * | 2004-08-12 | 2006-08-17 | Clariant Gmbh | Flame-retardant polymers with glow-wire resistance |
| CN1940014A (en) * | 2006-09-29 | 2007-04-04 | 公安部四川消防研究所 | Whiteness microcapsule red phosphorus and its production |
| CN101503568A (en) * | 2008-02-04 | 2009-08-12 | 金发科技股份有限公司 | Red phosphorus flame-retardant enhanced thermoplastic polyamide composition |
| CN102775814A (en) * | 2012-08-10 | 2012-11-14 | 四川省精细化工研究设计院 | Method for preparing micro-encapsulation red phosphorus |
| CN103980542A (en) * | 2014-05-30 | 2014-08-13 | 王万庆 | Method for preparing dust-free microencapsulated red phosphorus flame retardant |
| CN104017354A (en) * | 2014-06-09 | 2014-09-03 | 温州科力塑业有限公司 | Halogen-free red phosphorus flame retardant nylon with high toughness and preparation method of nylon |
| CN104059388A (en) * | 2014-06-27 | 2014-09-24 | 南京化工职业技术学院 | Double-coated microencapsulated red phosphorus and preparation method thereof |
| CN105295101A (en) * | 2015-12-01 | 2016-02-03 | 中国科学技术大学苏州研究院 | Microencapsulated red phosphorus fire retardant and preparation method and application thereof |
| CN106009045A (en) * | 2016-07-01 | 2016-10-12 | 中国科学院宁波材料技术与工程研究所 | Microencapsulated red phosphorus, and preparation method and application thereof |
| CN109971039A (en) * | 2019-04-09 | 2019-07-05 | 东北林业大学 | A kind of preparation method of modified melamine-formaldehyde resin encapsulated red phosphorus |
Non-Patent Citations (2)
| Title |
|---|
| HAITAO WANG ET AL.: "A simple route for the preparation of red phosphorus microcapsule with fine particle distribution", 《MATERIALS LETTERS》 * |
| 程晨等: "密胺甲醛树脂微胶囊红磷的制备及安定性研究", 《塑料工业》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112646366A (en) * | 2020-12-22 | 2021-04-13 | 江苏集萃先进高分子材料研究所有限公司 | Halogen-free environment-friendly flame-retardant master batch of long glass fiber reinforced nylon composite material and preparation method thereof |
| CN113214542A (en) * | 2021-05-18 | 2021-08-06 | 湖南娄底华星锑业有限公司 | Composite antimony trioxide flame retardant and preparation method thereof |
| CN113214542B (en) * | 2021-05-18 | 2022-05-20 | 湖南娄底华星锑业有限公司 | Composite antimony trioxide flame retardant and preparation method thereof |
| CN116462930A (en) * | 2023-04-06 | 2023-07-21 | 青岛中新华美塑料有限公司 | Flame-retardant ABS alloy material and preparation method thereof |
| CN116462930B (en) * | 2023-04-06 | 2024-01-19 | 青岛中新华美塑料有限公司 | Flame-retardant ABS alloy material and preparation method thereof |
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Effective date of registration: 20230515 Address after: Haojia Village Industrial Park, Liangqiu Town, Fei County, Linyi City, Shandong Province, 273400 Patentee after: Linyi senmeite Wood Industry Co.,Ltd. Address before: 250014 No. 19, ASTRI Road, Lixia District, Shandong, Ji'nan Patentee before: ENERGY Research Institute OF SHANDONG ACADEMY OF SCIENCES |