CN102660059B - Preparation method of flame-resistant polyolefin composite - Google Patents
Preparation method of flame-resistant polyolefin composite Download PDFInfo
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- CN102660059B CN102660059B CN201210149170.7A CN201210149170A CN102660059B CN 102660059 B CN102660059 B CN 102660059B CN 201210149170 A CN201210149170 A CN 201210149170A CN 102660059 B CN102660059 B CN 102660059B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention discloses a preparation method of a flame-resistant polyolefin composite. The flame-resistant polyolefin composite comprises the following components in parts by weight: 100 parts of polyolefin resin, 15-30 parts of ammonium polyphosphate, 1-6 parts of 2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazine, 1-6 parts of branched polymer containing nitrogen and phosphorus, 0.1-0.7 part of antioxygen and 0.4-0.8 part of lubricant; and the preparation method comprises the following steps of: evenly mixing and compounding ammonium polyphosphate, 2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazine and branched polymer containing nitrogen and phosphorus at the temperature of 100-130 DEG C, evenly mixing with the polyolefin resin, the antioxygen and the lubricant, and extruding and pelleting by virtue of a screw rod at the temperature of 130-220 DEG C. The flame-resistant polyolefin composite disclosed by the invention is free from halogen flame-resistant components, is good in expansion flame resistant performance, and is capable of meeting the requirement of environmentally-friendly flame resistance.
Description
Technical field
The present invention relates to the flame-retarded technology of superpolymer, particularly relate to a kind of anti-flaming polyolefin composition and preparation method thereof.
Background technology
Polyolefinic limit oxygen number is all lower, belongs to combustible material, and fire-retardant in many occasions is the prerequisite of their application.Halogen antimony synergistic is fire-retardant, has that consumption is few, efficiency is high, low cost and other advantages, is the Main Means of traditional commerce fire retardant polyolefin.But the fire-retardant persistence of easily bringing out of Halogen is polluted, increasingly by the arena of history that fades out, the Non-halogen Flame Retardant Technology of research and development green high-efficient just becomes the main flow in this field.Halogen-free expansion type flame-proof system take triazines material as core, is having potentiality aspect the efficient halogen-free anti-inflaming of superpolymer, has become for many years one of research focus of Green Flammability.
Halogen-free expansion type flame-proof system only has in the time that mate in source of the gas, acid source and three sources, charcoal source, could efficiently bring into play it to polyolefinic fire retardation.And collection coupling three comes from the material of one, existence is very limited naturally, and synthetic is also not easy very much, the actual finished industrial product that is often difficult to obtain them.The polycomponent Intumscent Flame Retardant System that multiple commercialization list source material is formed by rational proportion, through simple physical or chemical modification blend; not only raw material sources are extensive, preparation cost is cheap, convenient for processing and application; and be suitable for large-scale production, therefore industrial already by wide selection.
Be suitable for building single source material of halogen-free expansion type flame-proof system, mostly be the lower-molecular substance of strong polarity, the easily moisture absorption and difficult and superpolymer miscible, in the general easy generation bloom of use procedure, dialysis, and the problem such as deteriorated material over-all properties.Component polymer quantizes and the modification of component composite, can change component surface properties, increases the contact surface between component, improve interface interaction power, improve the comixing compatibility of flame-retardant system and superpolymer, reduce the transport phenomenas such as bloom and dialysis, and improve the performance such as resistant to extraction of product.
Summary of the invention
The object of the present invention is to provide a kind of anti-flaming polyolefin composition, its flame-retardant system has component polymer and quantizes and component composite Modification design, significantly overcome the phenomenon without easy bloom and dialysis before this design, and greatly improved the resistant to extraction performance of product.
Another object of the present invention is to provide a kind of preparation method of anti-flaming polyolefin composition.
Object of the present invention realizes by following technical scheme
A kind of anti-flaming polyolefin composition, is characterized in that being made up of following component by weight:
Above-mentioned Nitrogen-and Phosphorus-containing branched polymer refers to the polymkeric substance that has branched structure being reacted with two or three-functionality-degree P contained compound by TEAT and generate.Two described or three-functionality-degree P contained compound can be phosphorous acid diester, phosphorous dihalide or three oxyhalogen phosphorus.2,4,6-, tri-(N, N-dihydroxy ethyl) reaction mechanism of amido-1,3,5-triazines and phosphorous acid diester is ester interchange polymerization, and the alcohol that the reaction mechanism of it and phosphorous dichloride or phosphorus oxychloride is acyl chlorides depolymerizes, this area has many public technologies, can be by above-mentioned reaction mechanism by 2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines high molecular turns to described Nitrogen-and Phosphorus-containing branched polymer.The present invention is preferably reacted generated Nitrogen-and Phosphorus-containing branched polymer with diethyl phosphite generation ester interchange polymerization by TEAT.
Said polyolefins resin refers to polyvinyl resin, polyvinyl chloride (PVC) RESINS, polyvinyl alcohol resin, acrylic resin, polyacrylonitrile resin, polystyrene resin, polybutadiene, sovprene resin, polyisoprene resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, butadiene-styrene copolymer resin, perbutan resin, styrene-acrylonitrile copolymer resin, isobutylene-isoprene copolymer resin, ethylene-propylene-non-conjugated diene copolymer resin, styrene-butadiene-styrene resin or acrylonitrile-butadiene-styrene copolymer resin, or the mixing polyolefin resin that mixes of above-mentioned two or three polyolefin resin arbitrary proportion.
Above-mentioned oxidation inhibitor is single Hinered phenols antioxidant, or is the compound of Hinered phenols antioxidant and monothioester arbitrary proportion, or is the compound of Hinered phenols antioxidant, monothioester and the composite formation of aromatic amine oxidation inhibitor arbitrary proportion.The compound of described Hinered phenols antioxidant and monothioester, refers to by Hinered phenols antioxidant and the composite antioxidant systems forming of monothioester auxiliary antioxidant; Preferably by 2,6-di-tert-butyl-4-methy phenol, 2,2`-methylene-bis (4-methyl-6-tert-butylphenol), four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) the composite composite antioxidant system forming of monothioester auxiliary antioxidant of one of the Hinered phenols antioxidant of one of pentaerythritol ester, the positive stearyl alcohol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid and the two lauryl alcohol esters of thio-2 acid, thio-2 acid tetradecyl alcohol ester, the two stearyl alcohol esters of thio-2 acid.Described aromatic amine oxidation inhibitor is two fragrant secondary amine classes, Ursol D class or dihydroquinoline lopps; Preferably N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, two (4,4`-dioctyl) aniline, N-phenyl-N`-cyclohexyl Ursol D, N-sec.-propyl-N`-diphenyl-para-phenylene diamine, N-secondary octyl-N`-diphenyl-para-phenylene diamine, N-(1,3-dimethylbutyl)-N`-diphenyl-para-phenylene diamine, N, N`-diphenyl-para-phenylene diamine, N, N`-bis-(1-methyl) n-heptyl Ursol D, 4,4`-bis-(propyloxy phenyl base) pentanoic, N-cyclohexyl-p-ethoxyaniline or N-cyclohexyl-p-methoxyaniline.
Above-mentioned lubricant is stearic acid, Palmiticacid, tetradecanoic acid, the eicosanoic acid Huo docosoic of fatty acid, or the stearylamide of fatty acyl amide, palmitin acid amides, N, N`-methylene-bis stearylamide or N, N`-ethylenebisstearamide, or the stearyl alcohol of aliphatic alcohols or soft lipidol, or the butyl stearate of fatty acid ester or glyceryl monostearate, or the sodium stearate of metal soap, calcium stearate or Zinic stearas, or the methyl-silicone oil of silicone oil or ethyl silicon oil, or the ester type waxes of wax class, paraffin or polyethylene wax.
Anti-flaming polyolefin composition of the present invention, as follows preparation:
(1) metering takes each component raw material by weight ratio;
(2) ammonium polyphosphate, TEAT and Nitrogen-and Phosphorus-containing branched polymer three components are put into mixing equipment, at 100～130 ℃, mix;
(3) in mixing equipment, add again polyolefin resin, oxidation inhibitor and lubricant, continue to mix, obtain compound;
(4) compound is dropped into and extruded in processing units, at 130～220 ℃, extruding pelletization, obtains anti-flaming polyolefin composition.
2,4,6-, tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines has the triazine ring air source structure of polyhydric charcoal source structure and many nitrogen, there is good expandable flame retardant application potential quality, but still very rare for the public technology of fire retardant polyolefin about it so far.This is mainly because it is strong polarity, difficult and compatible polyolefin blend, and molecular weight is lower, easily causes bloom and dialysis problem.The present invention takes following technical measures, not only overcome the problems referred to above, but also improved 2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines is to polyolefinic flame retarding efficiency: (1) component polymer quantizes, by 2 of strong polarity, 4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazine high molecular turns to the weak Nitrogen-and Phosphorus-containing branched polymer of polarity, and by gained Nitrogen-and Phosphorus-containing branched polymer part alternative 2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines; (2) polycomponent synergistic, selects ammonium polyphosphate, TEAT and Nitrogen-and Phosphorus-containing branched polymer three components composite, forms the flame-retardant system of anti-flaming polyolefin composition of the present invention; (3) component composite modification, makes ammonium polyphosphate with TEAT together, first after Nitrogen-and Phosphorus-containing branched polymer blending and modifying, more compound with polyolefine.
Anti-flaming polyolefin composition of the present invention has good expandable flame retardant performance, ammonium polyphosphate wherein mainly plays acid source and action of gas source, 2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazine mainly plays charcoal source and action of gas source, Nitrogen-and Phosphorus-containing branched polymer held concurrently source of the gas, acid source and the effect of charcoal source.And anti-flaming polyolefin composition of the present invention, does not contain halogen flame retardant component, can meet the requirement of Green Flammability, its application prospect light.
Embodiment
By specific embodiment, the present invention is described in more detail or is described below, rather than limit the invention.
Embodiment 1
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: at room temperature, by the diethyl phosphite of the TEAT of 1.0mol solid, powdery and 4.5mol liquid state, be uniformly mixed into turbid liquid; Heating makes turbid liquid be warming up to 50 ± 1 ℃, reaction 1h, and turbid liquid becomes clear liquid; Continue heating and make clear liquid be warming up to 76 ± 1 ℃ of back flow reaction 5h, clear liquid becomes mucus; Reheat and make mucus be warming up to 103 ± 3 ℃, underpressure distillation reaction 7h, discharging, cooling, purify, obtain the Nitrogen-and Phosphorus-containing hyperbranched polymer a(NP-BP of 930.38g pale-yellow galss shape
a).
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate, 300g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BP
athree components are put into high-speed mixer, at 115 ℃, mix 3min, in high-speed mixer, add again 5000g polypropylene, 5g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g stearic acid, keep high-speed stirring to mix 6min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 170 ℃ ± 2, II district 175 ℃ ± 2, III district 180 ℃ ± 2, IV district 185 ℃ ± 2, V district 190 ℃ ± 2, VI district 195 ℃ ± 2, die head temperature is 200 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example A
1
The blank sample preparation of polypropylene: at 115 ℃, in high-speed mixer, add again 5000g polypropylene, 5g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g stearic acid, keep high-speed stirring to mix 6min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 170 ℃ ± 2, II district 175 ℃ ± 2, III district 180 ℃ ± 2, IV district 185 ℃ ± 2, V district 190 ℃ ± 2, VI district 195 ℃ ± 2, die head temperature is 200 ℃ ± 2, extrude, cooling, cutting, granulation, obtain the blank sample of polypropylene.
Comparative example A
2
Anti-flaming polypropylene composite preparation: 1250g ammonium polyphosphate is put into high-speed mixer, mix 3min at 115 ℃, in high-speed mixer, add again 5000g polypropylene, 5g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g stearic acid, keep high-speed stirring to mix 6min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 170 ℃ ± 2, II district 175 ℃ ± 2, III district 180 ℃ ± 2, IV district 185 ℃ ± 2, V district 190 ℃ ± 2, VI district 195 ℃ ± 2, die head temperature is 200 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example A
3
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate and 300g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines two components are put into high-speed mixer, mix 3min at 115 ℃, in high-speed mixer, add again 5000g polypropylene, 5g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g stearic acid, keep high-speed stirring to mix 6min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 170 ℃ ± 2, II district 175 ℃ ± 2, III district 180 ℃ ± 2, IV district 185 ℃ ± 2, V district 190 ℃ ± 2, VI district 195 ℃ ± 2, die head temperature is 200 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example A
4
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate and 300g NP-BP
athree components are put into high-speed mixer, at 115 ℃, mix 3min, in high-speed mixer, add again 5000g polypropylene, 5g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g stearic acid, keep high-speed stirring to mix 6min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 170 ℃ ± 2, II district 175 ℃ ± 2, III district 180 ℃ ± 2, IV district 185 ℃ ± 2, V district 190 ℃ ± 2, VI district 195 ℃ ± 2, die head temperature is 200 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, and complete the present embodiment and this comparative example A
1～A
4the performance test of sample, the results are shown in following table:
Upper table relatively shows: (1) PP is inflammable, uses separately APP can not effectively improve the UL-94 rank of PP, and APP and TEAT binary synergistic can make PP pass through V-2 level UL-94 test, but cause strong bloom, and the resistant to extraction of remarkable deteriorated PP composite sample; (2) the binary synergistic system that APP or it and TEAT form, first through NP-BP
aafter composite modification, more compound with PP, can not only avoid bloom phenomenon, but also can, in greatly improving resistance to draw, obviously improve the flame retardant properties of PP composite sample, can make its LOI value reach 33.7, UL-94 test by V-0 level.This means (1) NP-BP
a, TEAT and APP ternary synergistic be than single AP P or APP and TEAT binary synergistic, and PP is had to better fire retardation; (2) at NP-BP
a, NP-BP in TEAT and APP ternary synergistic system
acan play compatilizer effect, improve the consistency of they and PP.
Embodiment 2
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate, 210g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 210g NP-BP
athree components are put into high-speed mixer, at 115 ℃, mix 3min, in high-speed mixer, add again 5000g polypropylene, 5g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g stearic acid, keep high-speed stirring to mix 6min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 170 ℃ ± 2, II district 175 ℃ ± 2, III district 180 ℃ ± 2, IV district 185 ℃ ± 2, V district 190 ℃ ± 2, VI district 195 ℃ ± 2, die head temperature is 200 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, carry out performance test, and with embodiment 1 in comparative example A
1～A
4make comparisons, the results are shown in following table:
Upper table relatively shows: NP-BP
a, when TEAT and APP ternary synergistic, suitably reduce NP-BP
awith the consumption of TEAT, can not cause bloom, deteriorated resistant to extraction problem, and can keep the flame retardant properties of PP composite sample almost constant, LOI value reaches 33.7, UL-94 still by V-0 level.
Embodiment 3
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 750g ammonium polyphosphate, 300g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BP
athree components are put into high-speed mixer, at 100 ℃, mix 5min; In high-speed mixer, add again 5000g polypropylene, 6.5g2,6-di-tert-butyl-4-methy phenol and 20g polyethylene wax, keep high-speed stirring to mix 10min, obtain compound, compound is dropped in twin screw extruder, set extruder barrel each section of temperature: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, carry out performance test, and with embodiment 1 in comparative example A
1～A
4make comparisons, the results are shown in following table:
Upper table relatively shows: NP-BP
a, when TEAT and APP ternary synergistic, reduce in a large number APP consumption, may make the flame retardant properties of PP composite sample deteriorated, but still than there is no ternary synergistic fashion.
Embodiment 4
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 1500g ammonium polyphosphate, 50g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BP
athree components are put into high-speed mixer, at 130 ℃, mix 1min, in high-speed mixer, add again 5000g polypropylene, 10g β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid, the two stearyl alcohol esters of 15g thio-2 acid and 20g calcium stearate, keep high-speed stirring to mix 1min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 175 ℃ ± 2, II district 180 ℃ ± 2, III district 185 ℃ ± 2, IV district 190 ℃ ± 2, V district 195 ℃ ± 2, VI district 200 ℃ ± 2, die head temperature is 205 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, carry out performance test, and make comparisons with the comparative example A 1～A4 in embodiment 1, the results are shown in following table:
Upper table relatively shows: NP-BP
a, when TEAT and APP ternary synergistic, in the time of the proportional Incomplete matching of tlv triple, may make the flame retardant properties of PP composite sample deteriorated, but still than there is no ternary synergistic fashion.
Embodiment 5
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 1500g ammonium polyphosphate, 300g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 50g NP-BP
athree components are put into high-speed mixer, at 130 ℃, mix 2min, in high-speed mixer, add again 5000g polypropylene, 10g β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid, the two lauryl alcohol esters of 20g thio-2 acid and 40g stearyl alcohol, keep high-speed stirring to mix 2min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 180 ℃ ± 2, II district 185 ℃ ± 2, III district 190 ℃ ± 2, IV district 195 ℃ ± 2, V district 200 ℃ ± 2, VI district 205 ℃ ± 2, die head temperature is 210 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, carry out performance test, and with embodiment 1 in comparative example A
1～A
4make comparisons, the results are shown in following table:
Upper table relatively shows: NP-BP
a, when TEAT and APP ternary synergistic, the proportional Incomplete matching of tlv triple, and NP-BP
awhen consumption is less, may make resistant to extraction performance and the flame retardant properties of PP composite sample deteriorated, but its flame retardant properties is still than there is no ternary synergistic fashion.
Embodiment 6
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 1500g ammonium polyphosphate, 75g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 125g NP-BP
athree components are put into high-speed mixer, at 130 ℃, mix 1min, in high-speed mixer, add again 5000g polypropylene, 11g β-(3, 5-di-tert-butyl-hydroxy phenyl) the positive stearyl alcohol ester of propionic acid, the two lauryl alcohol esters of 24g thio-2 acid and 35g stearylamide, keep high-speed stirring to mix 2min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 180 ℃ ± 2, II district 185 ℃ ± 2, III district 190 ℃ ± 2, IV district 195 ℃ ± 2, V district 200 ℃ ± 2, VI district 205 ℃ ± 2, die head temperature is 210 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, carry out performance test, and with embodiment 1 in comparative example A
1～A
4make comparisons, the results are shown in following table.
Upper table relatively shows: NP-BP
a, when TEAT and APP ternary synergistic, in the time of the proportional coupling of tlv triple, suitably reduce NP-BP
aimprove APP consumption with TEAT consumption, can guarantee that the flame retardant properties of PP composite sample is not deteriorated, but can make the resistant to extraction variation of PP composite sample, but its resistant to extraction is still than there is no ternary synergistic fashion.
Embodiment 7
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate, 250g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 200g NP-BP
athree components are put into high-speed mixer, at 115 ℃, mix 3min, in high-speed mixer, add again 4500g polypropylene, 500g polyethylene, 5g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two stearyl alcohol esters of 10g thio-2 acid and 25g Zinic stearas, keep high-speed stirring to mix 7min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example B
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate, 250g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines, 200g NP-BP
a, 4500g polypropylene, 500g polyethylene, 5g tetra-(β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) the two stearyl alcohol esters of pentaerythritol ester, 10g thio-2 acid and 25g Zinic stearas, put into high-speed mixer, at 115 ℃, mix 10min and obtain compound; Compound is dropped in twin screw extruder, set extruder barrel each section of temperature: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, and complete the performance test of the present embodiment and this comparative example B sample, the results are shown in following table:
The maximum difference of this comparative example B and the present embodiment is: the former is disposable each component raw material input, the first composite modified flame-retardant of the latter system component NP-BP
a, TEAT and APP, then drop into other component raw material.Upper table relatively shows: by first through NP-BP to TEAT and APP
ablending and modifying, is conducive to improve they and polyolefinic consistency, can eliminate bloom phenomenon, and improve resistant to extraction.
Embodiment 8
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate, 200g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BP
athree components are put into high-speed mixer, at 115 ℃, mix 4min, in high-speed mixer, add again 4000g polypropylene, 500g polystyrene, 500g styrene-butadiene-styrene block copolymer, 8g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 20g thio-2 acid tetradecyl alcohol ester and 30g glyceryl monostearate, keep high-speed stirring to mix 8min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example C
Anti-flaming polypropylene composite preparation: by 1250g ammonium polyphosphate, 200g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines, 300g NP-BP
a, 4000g polypropylene, 500g polystyrene, 500g styrene-butadiene-styrene block copolymer, 8g tetra-(β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 20g thio-2 acid tetradecyl alcohol ester and 30g glyceryl monostearate, put into high-speed mixer, at 115 ℃, mix 12min, obtain compound; Compound is dropped in twin screw extruder, set extruder barrel each section of temperature: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, and complete the performance test of the present embodiment and this comparative example C sample, result is as following table:
The maximum difference of this comparative example C and the present embodiment is: the former is disposable each component raw material input, the first composite modified flame-retardant of the latter system component NP-BP
a, TEAT and APP, then drop into other component raw material.Upper table relatively shows: by first through NP-BP to TEAT and APP
ablending and modifying, is conducive to improve they and polyolefinic consistency, can eliminate bloom phenomenon, and improve resistant to extraction.
Embodiment 9
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with phosphorus oxychloride, 2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines is main raw material, the method of recording with reference to Chinese patent CN101475683B, prepares Nitrogen-and Phosphorus-containing flame-retardant hyperbranched polymer b(NP-BP
b).
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: by 1300g ammonium polyphosphate, 225g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 240g NP-BP
bthree components are put into high-speed mixer, at 115 ℃, mix 4min, in high-speed mixer, add again 5000g acrylonitrile-butadiene-styrene copolymer, 6g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 14g thio-2 acid lauryl alcohol ester and 20g polyethylene wax, keep high-speed stirring to mix 9min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example D
1
The blank sample preparation of acrylonitrile-butadiene-styrene copolymer: at 115 ℃, in high-speed mixer, add again 5000g acrylonitrile-butadiene-styrene copolymer, 6g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 14g thio-2 acid lauryl alcohol ester and 20g polyethylene wax, keep high-speed stirring to mix 9min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example D
2
Fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture preparation: 1300g ammonium polyphosphate is put into high-speed mixer, mix 4min at 115 ℃, in high-speed mixer, add again 5000g acrylonitrile-butadiene-styrene copolymer, 6g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 14g thio-2 acid lauryl alcohol ester and 20g polyethylene wax, keep high-speed stirring to mix 9min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, and complete the present embodiment and this comparative example D
1, D
2the performance test of sample, result is as following table.
Upper table relatively shows: (1) ABS is inflammable, uses separately APP can not effectively improve the UL-94 rank of ABS; (2) NP-BP
b, TEAT and APP ternary synergistic have significant fire retardation to ABS, make its LOI value be increased to 32.3, UL-94 by 17.8 and test by rise to V-0 level without rank; (3) NP-BP
b, the first blending and modifying of TEAT and APP ternary, then with ABS blend, can eliminate bloom phenomenon.
Embodiment 10
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 9.
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: by 1250g ammonium polyphosphate, 190g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 200g NP-BP
bthree components are put into high-speed mixer, at 120 ℃, mix 3min, in high-speed mixer, add again 4750g acrylonitrile-butadiene-styrene copolymer, 250g polyvinyl chloride, 8g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 17g thio-2 acid stearyl alcohol ester and 40g Zinic stearas, keep high-speed stirring to mix 7min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example E
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: by 1250g ammonium polyphosphate, 190g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines, 200g NP-BP
b, 4750g acrylonitrile-butadiene-styrene copolymer, 250g polyvinyl chloride, 8g tetra-(β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 17g thio-2 acid stearyl alcohol ester and 40g Zinic stearas, put into high-speed mixer, at 120 ℃, mix 10min, obtain compound; Compound is dropped in twin screw extruder, set extruder barrel each section of temperature: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, and complete the performance test of the present embodiment and this comparative example E sample, result is as following table:
The maximum difference of this comparative example E and the present embodiment is: the former is disposable each component raw material input, the first composite modified flame-retardant of the latter system component NP-BP
a, TEAT and APP, then drop into other component raw material.Upper table relatively shows: by first through NP-BP to TEAT and APP
bblending and modifying, is conducive to improve they and polyolefinic consistency, can eliminate bloom phenomenon, and improve resistant to extraction.
Embodiment 11
Synthesizing of Nitrogen-and Phosphorus-containing branched polymer: with embodiment 9.
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: by 1300g ammonium polyphosphate, 225g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines and 240g NP-BP
bthree components are put into Banbury mixer, at 125 ℃, mix 3min, in Banbury mixer, add again 4000g acrylonitrile-butadiene-styrene copolymer, 250g polyvinyl chloride, 750g ternary ethylene-propylene copolymer resin, 9g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 16g thio-2 acid stearyl alcohol ester, 5g N-phenyl-N`-cyclohexyl Ursol D and 40g Zinic stearas, keep high speed banburying 3min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Comparative example F
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: by 1300g ammonium polyphosphate, 225g2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines, 240g NP-BP
b, 4000g acrylonitrile-butadiene-styrene copolymer, 250g polyvinyl chloride, 750g ternary ethylene-propylene copolymer resin, 9g tetra-(β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, 16g thio-2 acid stearyl alcohol ester, 5g N-phenyl-N`-cyclohexyl Ursol D and 40g Zinic stearas, put into Banbury mixer, at 125 ℃, mix 6min, obtain compound, compound is dropped in twin screw extruder, set each section of temperature of extruder barrel: I district is 165 ℃ ± 2, II district 170 ℃ ± 2, III district 175 ℃ ± 2, IV district 180 ℃ ± 2, V district 185 ℃ ± 2, VI district 190 ℃ ± 2, die head temperature is 195 ℃ ± 2, extrude, cooling, cutting, granulation, obtain anti-flaming polyolefin composition.
Prepare batten according to GB injection moulding, and complete the performance test of the present embodiment and this comparative example F sample, result is as following table:
The maximum difference of this comparative example F and the present embodiment is: the former is disposable each component raw material input, the first composite modified flame-retardant of the latter system component NP-BP
a, TEAT and APP, then drop into other component raw material.Upper table relatively shows: by first through NP-BP to TEAT and APP
bblending and modifying, is conducive to improve they and polyolefinic consistency, can eliminate bloom phenomenon, and improve resistant to extraction.
In specification sheets of the present invention, APP=ammonium polyphosphate, PP=polypropylene, PE=polyethylene, PS=polystyrene, PVC=polyvinyl chloride, SBS=styrene-butadiene-styrene block copolymer, ABS=acrylonitrile-butadiene-styrene copolymer, TEAT=2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazine, EPDM=ternary ethylene-propylene copolymer resin, NP-BP
a=press method described in embodiment 1 obtain Nitrogen-and Phosphorus-containing branched polymer, NP-BP
b=press method described in embodiment 8 obtain Nitrogen-and Phosphorus-containing branched polymer.
Claims (9)
1. a preparation method for anti-flaming polyolefin composition, is characterized in that
(1) consist of by weight:
Polyolefin resin 100
Ammonium polyphosphate 15 ~ 30
TEAT 1 ~ 6
Nitrogen-and Phosphorus-containing branched polymer 1 ~ 6
Oxidation inhibitor 0.1 ~ 0.7
Lubricant 0.4 ~ 0.8;
(2) preparation method
Metering by weight ratio takes each component raw material; Ammonium polyphosphate, TEAT and Nitrogen-and Phosphorus-containing branched polymer three components are put into mixing equipment, at 100～130 ℃, mix; In mixing equipment, add again polyolefin resin, oxidation inhibitor and lubricant, continue to mix, obtain compound; Compound is dropped into and extruded in processing units, and at 130～220 ℃, extruding pelletization, obtains anti-flaming polyolefin composition;
Described Nitrogen-and Phosphorus-containing branched polymer refers to and is reacted the polymkeric substance that has branched structure generating by TEAT with two or three-functionality-degree P contained compound; Two described or three-functionality-degree P contained compound is phosphorous acid diester, phosphorous dihalide or three oxyhalogen phosphorus.
2. the preparation method of a kind of anti-flaming polyolefin composition according to claim 1, it is characterized in that described polyolefin resin refers to polyvinyl resin, acrylic resin, polystyrene resin, polybutadiene, polyisoprene resin, ethylene-propylene copolymer resin, butadiene-styrene copolymer resin, isobutylene-isoprene copolymer resin, ethylene-propylene-non-conjugated diene copolymer resin or styrene-butadiene-styrene resin, or the mixing polyolefin resin that mixes of above-mentioned two or three polyolefin resin arbitrary proportion.
3. the preparation method of a kind of anti-flaming polyolefin composition according to claim 1, it is characterized in that described oxidation inhibitor is single Hinered phenols antioxidant, or be the compound of Hinered phenols antioxidant and monothioester arbitrary proportion, or be the compound of Hinered phenols antioxidant, monothioester and the composite formation of aromatic amine oxidation inhibitor arbitrary proportion.
4. the preparation method of a kind of anti-flaming polyolefin composition according to claim 3, it is characterized in that described Hinered phenols antioxidant, refer to 2,6-di-tert-butyl-4-methy phenol, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester or the positive stearyl alcohol ester of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid.
5. the preparation method of a kind of anti-flaming polyolefin composition according to claim 3, is characterized in that described monothioester, refers to the two lauryl alcohol esters of thio-2 acid, thio-2 acid tetradecyl alcohol ester or the two stearyl alcohol esters of thio-2 acid.
6. the preparation method of a kind of anti-flaming polyolefin composition according to claim 3, is characterized in that described aromatic amine oxidation inhibitor is two fragrant secondary amine classes, Ursol D class or dihydroquinoline lopps.
7. the preparation method of a kind of anti-flaming polyolefin composition according to claim 6, it is characterized in that two described fragrant secondary amine classes refer to oxidation inhibitor N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 4,4 '-bis-(propyloxy phenyl base) pentanoic, N-cyclohexyl-p-ethoxyaniline or N-cyclohexyl-p-methoxyaniline.
8. the preparation method of a kind of anti-flaming polyolefin composition according to claim 6, it is characterized in that described Ursol D class refers to oxidation inhibitor N-phenyl-N '-cyclohexyl Ursol D, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N-secondary octyl-N '-diphenyl-para-phenylene diamine, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, N, N '-diphenyl-para-phenylene diamine or N, N '-bis-(1-methyl) n-heptyl Ursol D.
9. the preparation method of a kind of anti-flaming polyolefin composition according to claim 1, it is characterized in that the stearic acid that described lubricant is fatty acid, Palmiticacid, tetradecanoic acid, eicosanoic acid Huo docosoic, or the stearylamide of fatty acyl amide, palmitin acid amides, N, N '-methylene-bis stearylamide or N, N '-ethylenebisstearamide, or the stearyl alcohol of aliphatic alcohols or soft lipidol, or the butyl stearate of fatty acid ester or glyceryl monostearate, or the sodium stearate of metal soap, calcium stearate or Zinic stearas, or the methyl-silicone oil of silicone oil or ethyl silicon oil, or the ester type waxes of wax class, paraffin or polyethylene wax.
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| CN106700381A (en) * | 2016-12-13 | 2017-05-24 | 德阳力久云智知识产权运营有限公司 | SBS-containing flame-retardant modified plastic and preparation method thereof |
| CN109575552A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Functional flame-retardant high-molecular composition and its preparation method and application |
| CN108912549A (en) * | 2018-07-18 | 2018-11-30 | 曹佳男 | A kind of highly effective flame-retardant type PVC floor and preparation method thereof |
| CN112248273A (en) * | 2020-08-04 | 2021-01-22 | 南通瑞诚高分子材料有限公司 | Bidirectional modification process for plastic particles |
| CN116829641A (en) * | 2020-08-13 | 2023-09-29 | 陶氏环球技术有限责任公司 | Halogen-free flame retardant elastomer composition, articles prepared therefrom and method of preparing the same |
| CN115678291B (en) * | 2021-07-27 | 2023-10-10 | 中国石油化工股份有限公司 | Anti-falling agent and preparation method and application thereof |
| CN115679470B (en) * | 2022-12-08 | 2024-05-24 | 普宁市耿晟织造有限公司 | Flame-retardant polyester fiber fabric and preparation method thereof |
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| CN102225952A (en) * | 2011-04-05 | 2011-10-26 | 刘方旭 | Tris-(N,N-dihydroxyethylamino)-s-triazine phosphate ester fire retardant and preparation method thereof |
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