CN102660059A - Preparation method of flame-resistant polyolefin composite - Google Patents
Preparation method of flame-resistant polyolefin composite Download PDFInfo
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- CN102660059A CN102660059A CN2012101491707A CN201210149170A CN102660059A CN 102660059 A CN102660059 A CN 102660059A CN 2012101491707 A CN2012101491707 A CN 2012101491707A CN 201210149170 A CN201210149170 A CN 201210149170A CN 102660059 A CN102660059 A CN 102660059A
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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 average is lower, belongs to combustible material, and fire-retardant in many occasions is the prerequisite that they are used.Halogen antimony synergistic is fire-retardant, has that consumption is few, efficient is high, low cost and other advantages, is the main means of conventional commercial fire retardant polyolefin.Yet Halogen is fire-retardant to be prone to bring out persistence and to pollute, and day by day 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.With the triazines material is the halogen-free expansion type flame-proof system of core, is having potentiality aspect the efficient halogen-free anti-inflaming of superpolymer, has become one of green fire-retardant research focus for many years.
The halogen-free expansion type flame-proof system has only when source of the gas, acid source and three sources, charcoal source coupling, could efficiently bring into play it to polyolefinic fire retardation.And collection coupling three comes from the material of one, exists ten minutes limited naturally, and synthetic also is not easy very much, the actual finished industrial product that often is difficult to obtain them.The polycomponent expansion type flame-retarding system that the single source of multiple commercialization 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 in industry already by wide selection.
Be suitable for making up single source material of halogen-free expansion type flame-proof system, be mostly strong polar lower-molecular substance, be prone to the moisture absorption and difficult dissolving with superpolymer mixed, generally be prone to generation bloom, dialysis in use, and problem such as deterioration material over-all properties.Quantification of component polymer and component blend are composite modified, can change the component surface properties, increase the contact surface between component; Improve interface interaction power; Improve the comixing compatibility of flame-retardant system and superpolymer, reduce transport phenomenas such as bloom and dialysis, and improve the performances 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 the component polymer and quantizes and the composite modified design of component blend; Significantly having overcome does not have the preceding phenomenon that is prone to bloom and dialysis of this design, and has improved the resistant to extraction performance of product greatly.
Another object of the present invention is to provide a kind of preparation method of anti-flaming polyolefin composition.
The object of the invention is realized 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 nitrogenous phosphorus branched polymer is meant by 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and two or the reaction of three-functionality-degree P contained compound and the polymkeric substance that has branched structure that generates.Described two or the three-functionality-degree P contained compound can be phosphorous acid diester, phosphorous dihalide or three oxyhalogen phosphorus.2,4,6-three (N, N-dihydroxy ethyl) amido-1; 3, the reaction mechanism of 5-triazine and phosphorous acid diester is an ester interchange polymerization, depolymerizes and the reaction mechanism of it and phosphorous dichloride or POCl3 is the alcohol of acyl chlorides, and this area has many public technologies; Can be through above-mentioned reaction mechanism with 2,4,6-three (N; The N-dihydroxy ethyl) amido-1,3,5-triazines HMW turns to described nitrogenous phosphorus branched polymer.The present invention is preferably by 2,4, and 6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and diethyl phosphite generation ester interchange polymerization react the nitrogenous phosphorus branched polymer that is generated.
The said polyolefins resin is meant polyvinyl resin, PVC RESINS, polyvinyl alcohol resin, acrylic resin, polyacrylonitrile resin, polystyrene resin, polybutadiene, sovprene resin, TR 301 resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, BS resin, perbutan resin, styrene-acrylonitrile copolymer resin, isobutylene-isoprene copolymer resin, ethylene-propylene-non-conjugated diene copolymer resin, styrene-butadiene-styrene copolymer 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 said Hinered phenols antioxidant and monothioester is meant by Hinered phenols antioxidant and the composite antioxidant systems that forms of monothioester auxiliary antioxidant; Preferably by 2; 6-di-tert-butyl-4-methy phenol, 2; 2`-methylene-bis (4-methyl-6-tert butyl phenol), four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) the composite composite antioxidant system that forms of monothioester auxiliary antioxidant of one of the two lauryl alcohol esters of Hinered phenols antioxidant of one of pentaerythritol ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) positive stearyl alcohol ester of propionic acid and thio-2 acid, thio-2 acid tetradecyl alcohol ester, the two stearyl alcohol esters of thio-2 acid propionic acid).Said aromatic amine oxidation inhibitor is two fragrant secondary amine classes, Ursol D class or EEDQ lopps; Preferred N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamines, two (4; The 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, the 3-dimethylbutyl)-N`-diphenyl-para-phenylene diamine, N, N`-diphenyl-para-phenylene diamine, N; N`-two (1-methyl) n-heptyl Ursol D, 4,4`-two (propyloxy phenyl base) pentanoic, N-cyclohexyl-p-ethoxyaniline or N-cyclohexyl-p-methoxyaniline.
Above-mentioned lubricant is Triple Pressed 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 VLTN 6 of aliphatic alcohols or soft lipidol; Or the butyl stearate of fatty acid ester or glyceryl monostearate; Or the StNa of metallic soap class, calcium stearate or Zinic stearas, or the methyl-silicone oil of silicone oil or ethyl silicon oil, or cured type ester type waxes, paraffin or polyethylene wax.
Anti-flaming polyolefin composition of the present invention can prepare as follows:
(1) metering takes by weighing each component raw material by weight ratio;
(2) with ammonium polyphosphate, 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and nitrogenous phosphorus branched polymer three components are put into mixing equipment, under 100～130 ℃, mix;
(3) in mixing equipment, add polyolefin resin, oxidation inhibitor and lubricant again, continue to mix, get compound;
(4) the compound input is extruded in the processing units, under 130～220 ℃, extruding pelletization gets anti-flaming polyolefin composition.
2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines has the triazine ring source of the gas structure of polyhydric charcoal source structure and many nitrogen, have good expandable flame retardant and use potential quality, but it is still very rare to be used for the public technology of fire retardant polyolefin about it so far.This mainly is because it is strong polarity, difficult and compatible polyolefin blend, and molecular weight is lower, causes bloom and dialysis problem easily.The present invention takes following technical measures, has not only overcome the problems referred to above, but also has improved 2,4,6-three (N; The N-dihydroxy ethyl) amido-1,3,5-triazines is to polyolefinic flame retarding efficiency: (1) component polymer quantizes, with strong polar 2,4; 6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines HMW turns to the more weak nitrogenous phosphorus branched polymer of polarity, and partly substitutes 2 with the nitrogenous phosphorus branched polymer of gained; 4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines; (2) polycomponent synergistic is selected ammonium polyphosphate, 2,4 for use, and 6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and nitrogenous phosphorus branched polymer three components are composite, constitutes the flame-retardant system of anti-flaming polyolefin composition of the present invention; (3) the component blend is composite modified, makes ammonium polyphosphate with 2,4, and 6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines together, and is behind nitrogenous phosphorus branched polymer blending and modifying, compound with polyolefine more earlier.
Anti-flaming polyolefin composition of the present invention has good expandable flame retardant performance, and ammonium polyphosphate wherein mainly plays acid source and action of gas source, 2; 4; 6-three (N, N-dihydroxy ethyl) amido-1,3; The 5-triazine mainly plays charcoal source and action of gas source, nitrogenous phosphorus branched polymer then 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 the halogen flame retardant component, can satisfy green fire-retardant requirement, and its application prospect is bright.
Embodiment
Below through concrete embodiment the present invention is described in more detail or describes, rather than limit the invention.
Embodiment 1
Synthesizing of nitrogenous phosphorus branched polymer: at room temperature, with 2,4 of 1.0mol solid, powdery, the diethyl phosphite that 6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 4.5mol are liquid mixes 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 makes mucus be warming up to 103 ± 3 ℃, underpressure distillation reaction 7h, discharging, cooling, purification, the nitrogenous phosphorus hyperbranched polymer a (NP-BP of 930.38g pale-yellow galss shape
a).
The anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate, 300g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BP
aThree components are put into high-speed mixer, mix 3min down in 115 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,5g four (β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g Triple Pressed Stearic Acid; Keep high-speed stirring to mix 6min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
The comparative example A 1
Vestolen PP 7052 blank preparation: under 115 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,5g four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g Triple Pressed Stearic Acid again, keep high-speed stirring to mix 6min; Get compound; Compound is dropped in the twin screw extruder, set each section of extruder barrel temperature: the 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, and die head temperature is 200 ℃ ± 2; Extrude, cool off, cutting, granulation, the Vestolen PP 7052 blank.
The comparative example A 2
Anti-flaming polypropylene composite preparation: the 1250g ammonium polyphosphate is put into high-speed mixer, mix 3min down in 115 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,5g four (β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g Triple Pressed Stearic Acid; Keep high-speed stirring to mix 6min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
The comparative example A 3
The anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate and 300g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines two components are put into high-speed mixer, mix 3min down in 115 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,5g four (β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g Triple Pressed Stearic Acid; Keep high-speed stirring to mix 6min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
The comparative example A 4
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
Anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate and 300g NP-BP
aThree components are put into high-speed mixer, mix 3min down in 115 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,5g four (β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g Triple Pressed Stearic Acid; Keep high-speed stirring to mix 6min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, and accomplish present embodiment and this comparative example A
1~ A
4The performance test of sample, the result sees the following form:
Last table comparison shows that: (1) PP is inflammable, uses APP can not effectively improve the UL-94 rank of PP separately, 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 deterioration PP composite sample; (2) the binary synergistic system that constitutes of APP or it and TEAT is earlier through NP-BP
aAfter blend is composite modified, compound with PP again, can not only avoid the bloom phenomenon, but also can when improving resistance to draw greatly, obviously improve the flame retardant properties of PP composite sample, can make its LOI value reach 33.7, the UL-94 test is through the 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 better fire retardation; (2) at NP-BP
a, NP-BP in TEAT and the APP ternary synergistic system
aCan play the compatilizer effect, improve the consistency of they and PP.
Embodiment 2
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
The anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate, 210g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 210g NP-BP
aThree components are put into high-speed mixer, mix 3min down in 115 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,5g four (β-(3 again; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two lauryl alcohol esters of 10g thio-2 acid and 30g Triple Pressed Stearic Acid; Keep high-speed stirring to mix 6min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, carry out performance test, and with embodiment 1 in the comparative example A
1~ A
4Make comparisons, the result sees the following form:
Last table comparison shows that: NP-BP
a, when TEAT and APP ternary synergistic, suitably reduce NP-BP
aWith the consumption of TEAT, can not cause bloom, deterioration resistant to extraction problem, and can keep the flame retardant properties of PP composite sample almost constant, the LOI value reaches 33.7, and UL-94 is still through the V-0 level.
Embodiment 3
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
The anti-flaming polypropylene composite preparation: with 750g ammonium polyphosphate, 300g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BP
aThree components are put into high-speed mixer, mix 5min down in 100 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,6.5g 2 again; 6-di-tert-butyl-4-methy phenol and 20g polyethylene wax; Keep high-speed stirring to mix 10min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, carry out performance test, and with embodiment 1 in the comparative example A
1~ A
4Make comparisons, the result sees the following form:
Last table comparison shows that: NP-BP
a, when TEAT and APP ternary synergistic, reduce the APP consumption in a large number, may make the flame retardant properties deterioration of PP composite sample, but still than there not being ternary synergistic fashion.
Embodiment 4
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
The anti-flaming polypropylene composite preparation: with 1500g ammonium polyphosphate, 50g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BP
aThree components are put into high-speed mixer, mix 1min down in 130 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,10g β-(3 again; The 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, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, carry out performance test, and with embodiment 1 in the comparative example A
1~ A
4Make comparisons, the result sees the following form:
Last table comparison shows that: NP-BP
a, when TEAT and APP ternary synergistic, when the proportional incomplete coupling of tlv triple, may make the flame retardant properties deterioration of PP composite sample, but still than there not being ternary synergistic fashion.
Embodiment 5
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
The anti-flaming polypropylene composite preparation: with 1500g ammonium polyphosphate, 300g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 50g NP-BP
aThree components are put into high-speed mixer, mix 2min down in 130 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,10g β-(3 again; The 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 VLTN 6; Keep high-speed stirring to mix 2min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, carry out performance test, and with embodiment 1 in the comparative example A
1~ A
4Make comparisons, the result sees the following form:
Last table comparison shows that: NP-BP
a, when TEAT and APP ternary synergistic, the proportional incomplete coupling of tlv triple, and NP-BP
aConsumption may make the resistant to extraction performance and the flame retardant properties deterioration of PP composite sample more after a little while, but its flame retardant properties is still than there not being ternary synergistic fashion.
Embodiment 6
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
The anti-flaming polypropylene composite preparation: with 1500g ammonium polyphosphate, 75g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 125g NP-BP
aThree components are put into high-speed mixer, mix 1min down in 130 ℃; In high-speed mixer, add 5000g Vestolen PP 7052,11g β-(3 again; The 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, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, carry out performance test, and with embodiment 1 in the comparative example A
1~ A
4Make comparisons, the result sees the following form.
Last table comparison shows that: NP-BP
a, when TEAT and APP ternary synergistic, when the proportional coupling of tlv triple, suitably reduce NP-BP
aImprove the APP consumption with the TEAT consumption, the flame retardant properties that can guarantee the PP composite sample is deterioration not, but can make the resistant to extraction variation of PP composite sample, but its resistant to extraction is still than there not being ternary synergistic fashion.
Embodiment 7
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
The anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate, 250g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 200g NP-BP
aThree components are put into high-speed mixer, mix 3min down in 115 ℃; In high-speed mixer, add 4500g Vestolen PP 7052,500g Vilaterm, 5g four (β-(3 again; The 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, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Comparative Examples B
The anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate, 250g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines, 200gNP-BP
a, 4500g Vestolen PP 7052,500g Vilaterm, 5g four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, the two stearyl alcohol esters of 10g thio-2 acid and 25g Zinic stearas; Put into high-speed mixer, mix 10min down in 115 ℃ and get compound; Compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, and accomplish the performance test of present embodiment and this Comparative Examples B sample, the result sees the following form:
The difference of the maximum of this Comparative Examples B and present embodiment is: the former is the disposable input of each component raw material, the composite modified flame-retardant system component of latter's elder generation's blend NP-BP
a, TEAT and APP, drop into other component raw material again.Last table comparison shows that: TEAT and APP is first through NP-BP
aBlending and modifying helps improving they and polyolefinic consistency, can eliminate the bloom phenomenon, and improve resistant to extraction.
Embodiment 8
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 1.
The anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate, 200g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 300g NP-BPa three components are put into high-speed mixer, mix 4min down in 115 ℃; In high-speed mixer, add 4000g Vestolen PP 7052,500g PS, 500g styrene-butadiene-styrene block copolymer, 8g four (β-(3 again; The 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; Get compound; Compound is dropped in the twin screw extruder, set each section of extruder barrel temperature: the 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, and die head temperature is 195 ℃ ± 2; Extrude, cool off, cutting, granulation, anti-flaming polyolefin composition.
Comparative Examples C
The anti-flaming polypropylene composite preparation: with 1250g ammonium polyphosphate, 200g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines, 300g NP-BP
a, 4000g Vestolen PP 7052,500g PS, 500g styrene-butadiene-styrene block copolymer, 8g four (β-(3; The 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; Under 115 ℃, mix 12min, get compound; Compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, and accomplish the performance test of present embodiment and this Comparative Examples C sample, result such as following table:
The difference of the maximum of this Comparative Examples C and present embodiment is: the former is the disposable input of each component raw material, the composite modified flame-retardant system component of latter's elder generation's blend NP-BP
a, TEAT and APP, drop into other component raw material again.Last table comparison shows that: TEAT and APP is first through NP-BP
aBlending and modifying helps improving they and polyolefinic consistency, can eliminate the bloom phenomenon, and improve resistant to extraction.
Embodiment 9
Synthesizing of nitrogenous phosphorus branched polymer: with POCl3,2,4,6-three (N, N-hydroxyethyl) amido-1,3,5-triazines is a main raw material, and the method with reference to Chinese patent CN 101475683B record prepares nitrogenous phosphorus flame-retardant hyperbranched polymer b (NP-BP
b).
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: with 1300g ammonium polyphosphate, 225g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 240g NP-BP
bThree components are put into high-speed mixer, mix 4min down in 115 ℃; In high-speed mixer, add 5000g acrylonitrile-butadiene-styrene copolymer, 6g four (β-(3 again; The 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, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Comparative Examples D
1
Acrylonitrile-butadiene-styrene copolymer blank preparation: under 115 ℃; In high-speed mixer, add 5000g acrylonitrile-butadiene-styrene copolymer, 6g four (β-(3 again; The 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, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Comparative Examples D
2
Fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture preparation: the 1300g ammonium polyphosphate is put into high-speed mixer, mix 4min down in 115 ℃; In high-speed mixer, add 5000g acrylonitrile-butadiene-styrene copolymer, 6g four (β-(3 again; The 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, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, and accomplish present embodiment and this Comparative Examples D
1, D
2The performance test of sample, result such as following table.
Last table comparison shows that: (1) ABS is inflammable, uses APP can not effectively improve the UL-94 rank of ABS separately; (2) NP-BP
b, TEAT and APP ternary synergistic have significant fire retardation to ABS, makes its LOI value be increased to 32.3 by 17.8, the UL-94 test rises to the V-0 level by no rank; (3) NP-BP
b, TEAT and APP ternary elder generation blending and modifying, with the ABS blend, can eliminate the bloom phenomenon again.
Embodiment 10
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 9.
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: with 1250g ammonium polyphosphate, 190g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 200g NP-BP
bThree components are put into high-speed mixer, mix 3min down in 120 ℃; In high-speed mixer, add 4750g acrylonitrile-butadiene-styrene copolymer, 250g SE, 8g four (β-(3 again; The 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, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Comparative Examples E
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: with 1250g ammonium polyphosphate, 190g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines, 200g NP-BP
b, 4750g acrylonitrile-butadiene-styrene copolymer, 250g SE, 8g four (β-(3; The 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; Under 120 ℃, mix 10min, get compound; Compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, and accomplish the performance test of present embodiment and this Comparative Examples E sample, result such as following table:
The difference of the maximum of this Comparative Examples E and present embodiment is: the former is the disposable input of each component raw material, the composite modified flame-retardant system component of latter's elder generation's blend NP-BP
a, TEAT and APP, drop into other component raw material again.Last table comparison shows that: TEAT and APP is first through NP-BP
bBlending and modifying helps improving they and polyolefinic consistency, can eliminate the bloom phenomenon, and improve resistant to extraction.
Embodiment 11
Synthesizing of nitrogenous phosphorus branched polymer: with embodiment 9.
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: with 1300g ammonium polyphosphate, 225g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and 240g NP-BP
bThree components are put into Banbury mixer, mix 3min down in 125 ℃; In Banbury mixer, add 4000g acrylonitrile-butadiene-styrene copolymer, 250g SE, 750g ternary ethylene-propylene copolymer resin, 9g four (β-(3 again; The 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; Get compound; Compound is dropped in the twin screw extruder, set each section of extruder barrel temperature: the 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, and die head temperature is 195 ℃ ± 2; Extrude, cool off, cutting, granulation, anti-flaming polyolefin composition.
Comparative Examples F
The preparation of fire-retardant acrylonitrile-butadiene diene-styrene copolymer mixture: with 1300g ammonium polyphosphate, 225g 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines, 240g NP-BP
b, 4000g acrylonitrile-butadiene-styrene copolymer, 250g SE, 750g ternary ethylene-propylene copolymer resin, 9g four (β-(3; The 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; Under 125 ℃, mix 6min, get compound, compound is dropped in the twin screw extruder; Set each section of extruder barrel temperature: the 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, cool off, cutting, granulation, anti-flaming polyolefin composition.
Prepare batten according to the GB injection moulding, and accomplish the performance test of present embodiment and this Comparative Examples F sample, result such as following table:
The difference of the maximum of this Comparative Examples F and present embodiment is: the former is the disposable input of each component raw material, the composite modified flame-retardant system component of latter's elder generation's blend NP-BP
a, TEAT and APP, drop into other component raw material again.Last table comparison shows that: TEAT and APP is first through NP-BP
bBlending and modifying helps improving they and polyolefinic consistency, can eliminate the bloom phenomenon, and improve resistant to extraction.
In the specification sheets of the present invention, APP=ammonium polyphosphate, PP=Vestolen PP 7052, PE=Vilaterm; The PS=PS, PVC=SE, SBS=styrene-butadiene-styrene block copolymer, ABS=acrylonitrile-butadiene-styrene copolymer; TEAT=2,4,6-three (N, N-dihydroxy ethyl) amido-1; 3,5-triazine, EPDM=ternary ethylene-propylene copolymer resin, NP-BP
a=nitrogenous phosphorus branched polymer that the method described in the embodiment 1 of pressing obtains, NP-BP
b=nitrogenous phosphorus branched polymer that the method described in the embodiment 8 of pressing obtains.
Claims (9)
1. the preparation method of an anti-flaming polyolefin composition is characterized in that
(1) consist of by weight:
(2) preparation method
Metering by weight ratio takes by weighing each component raw material; With ammonium polyphosphate, 2,4,6-three (N, N-dihydroxy ethyl) amido-1,3,5-triazines and nitrogenous phosphorus branched polymer three components are put into mixing equipment, under 100～130 ℃, mix; In mixing equipment, add polyolefin resin, oxidation inhibitor and lubricant again, continue to mix, get compound; The compound input is extruded in the processing units, and under 130～220 ℃, extruding pelletization gets anti-flaming polyolefin composition.
2. the preparation method of a kind of anti-flaming polyolefin composition according to claim 1; It is characterized in that described polyolefin resin is meant polyvinyl resin, PVC RESINS, polyvinyl alcohol resin, acrylic resin, polyacrylonitrile resin, polystyrene resin, polybutadiene, sovprene resin, TR 301 resin, ethylene-propylene copolymer resin, ethylene-vinyl acetate copolymer resin, BS resin, perbutan resin, styrene-acrylonitrile copolymer resin, isobutylene-isoprene copolymer resin, ethylene-propylene-non-conjugated diene copolymer resin, styrene-butadiene-styrene copolymer resin or acrylonitrile-butadiene-styrene copolymer 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 nitrogenous phosphorus branched polymer is meant by 2; 4,6-three (N, N-dihydroxy ethyl) amido-1; 3,5-triazine and two or the polymkeric substance that has branched structure that generates of three-functionality-degree P contained compound reaction.
4. the preparation method of a kind of anti-flaming polyolefin composition according to claim 3, it is characterized in that described two or the three-functionality-degree P contained compound can be phosphorous acid diester, phosphorous dihalide or three oxyhalogen phosphorus.
5. the preparation method of a kind of anti-flaming polyolefin composition according to claim 1; It is characterized in that said 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.
6. the preparation method of a kind of anti-flaming polyolefin composition according to claim 5; It is characterized in that described Hinered phenols antioxidant; Be meant 2,6 di tert butyl 4 methyl phenol, 2,2`-methylene-bis (4-methyl-6-tert butyl phenol), four (β-(3; The 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester or β-positive stearyl alcohol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid propionic acid).
7. the preparation method of a kind of anti-flaming polyolefin composition according to claim 5 is characterized in that described monothioester, is meant 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.
8. the preparation method of a kind of anti-flaming polyolefin composition according to claim 5 is characterized in that described aromatic amine oxidation inhibitor is two fragrant secondary amine classes, Ursol D class or EEDQ lopps; Preferred N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamines, two (4; The 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, the 3-dimethylbutyl)-N`-diphenyl-para-phenylene diamine, N, N`-diphenyl-para-phenylene diamine, N; N`-two (1-methyl) n-heptyl Ursol D, 4,4`-two (propyloxy phenyl base) pentanoic, N-cyclohexyl-p-ethoxyaniline or N-cyclohexyl-p-methoxyaniline.
9. the preparation method of a kind of anti-flaming polyolefin composition according to claim 1; It is characterized in that described lubricant is Triple Pressed 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; The N`-ethylenebisstearamide; Or the VLTN 6 of aliphatic alcohols or soft lipidol, or the butyl stearate of fatty acid ester or glyceryl monostearate, or the StNa of metallic soap class, calcium stearate or Zinic stearas; Or the methyl-silicone oil of silicone oil or ethyl silicon oil, or cured type ester type waxes, paraffin or polyethylene wax.
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| 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 |
| WO2022032554A1 (en) * | 2020-08-13 | 2022-02-17 | Dow Global Technologies Llc | Halogen free flame retardant elastomer composition, articles prepared from same and preparation methods thereof |
| CN115678291A (en) * | 2021-07-27 | 2023-02-03 | 中国石油化工股份有限公司 | Anti-shedding agent and preparation method and application thereof |
| 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 |
| CN115679470A (en) * | 2022-12-08 | 2023-02-03 | 胡洋兵 | Flame-retardant polyester fiber fabric and preparation method thereof |
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