CN102050987A - LDPE flame retardant composite material and preparation method thereof - Google Patents

LDPE flame retardant composite material and preparation method thereof Download PDF

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Publication number
CN102050987A
CN102050987A CN2010105590859A CN201010559085A CN102050987A CN 102050987 A CN102050987 A CN 102050987A CN 2010105590859 A CN2010105590859 A CN 2010105590859A CN 201010559085 A CN201010559085 A CN 201010559085A CN 102050987 A CN102050987 A CN 102050987A
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Prior art keywords
density polyethylene
low density
flame retardant
fire retardant
section
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CN2010105590859A
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CN102050987B (en
Inventor
林云青
张文霖
郝洪波
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Kangtai Plastic Science and Technology Group Co Ltd
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Kangtai Plastic Science and Technology Group Co Ltd
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Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • B29C2948/92904—Die; Nozzle zone

Abstract

The invention discloses LDPE (low density polyethylene) flame retardant composite material which is composed of following components by weight: 70 to 90 of linear LDPE, 10 to 20 of LDPE-g-MAH (maleic anhydride grafted low density polyethylene), 10 to 30 of melamine resin coated ammonium polyphosphate, 5 to 15 of pentaerythrite, 1 to 5 of montmorillonite, 660 to 110 of nylon and 1 to 4 of antioxidising agent. The invention further provides a preparation method of the LDPE flame retardant composite material. The flame retardant composite material prepared by the preparation method overcomes the defects of large combustion smog and more molten drops of halogenated flame retardant, low flame retardant efficiency, large additive amount and poor thermal stability and mechanical properties of materials of expanding type flame retardant. When the flame retardant property of the composite material is improved, the additive amount of the flame retardant is reduced, the mechanical properties of composite material are improved, and the requirement of practical application is satisfied.

Description

Low density polyethylene fire retardant matrix material and preparation method thereof
Technical field
The present invention relates to a kind of fire retardant material and preparation method thereof, be specifically related to a kind of low density polyethylene fire retardant matrix material and preparation method thereof.
Background technology
Fire retardant material is a kind of protecting materials, and it is can stop burning and own and be not easy the incendiary material, solid is arranged as saying materials such as cement, steel, glass; Have liquidly, also abbreviate fire retardant as, if coat fire retardant on various material surfaces such as need fire-proof wall, it can guarantee do not burnt on fire, can not make yet the combustion range aggravation, enlarge.At present, halogen containing flame-retardant commonly used, big, the many molten drop of its combustion fumes; And the expansion type flame retardant flame retarding efficiency is low, addition is bigger than normal, thermostability and material mechanical performance are poor, can not satisfy actual needs.
Summary of the invention
The object of the present invention is to provide a kind of novel expansion type flame retardant.
The present invention is achieved in that
A kind of low density polyethylene fire retardant matrix material, form by following component by weight:
Linear low density polyethylene: 70 to 90 parts; New LDPE (film grade) connects 10 to 20 parts of maleic anhydrides; 10 to 30 parts of melamine coated ammonium polyphosphates; 5 to 15 parts of tetramethylolmethanes; 1 to 5 part of polynite; 660 to 100 parts of nylon, 1 to 4 part of antioxidant.
Further scheme is: the density 0.915 of described linear low density polyethylene is to 0.930g/cm 3, melting index is not more than 2.5g/10min under 190 ℃, 2.16kg condition, and tensile yield strength is not less than 2.5MPa under the 50mm/min condition, and elongation at break is not less than 500% under the 50mm/min condition, and tensile break stress is not less than 12MPa.
Further scheme is: described new LDPE (film grade) meets the density 0.93g/cm of a maleic anhydride 3, melting index 0.8 is to 3.0g/10min under 190 ℃, 2.16kg condition, and 110 ℃ of Vicat softening points, the percentage of grafting of determination of acid-basetitration are 0.85%.
Further scheme is: the density 1.8g/cm of described melamine coated ammonium polyphosphate 3To 2.0g/cm 3, phosphorus content 28 to 30%, nitrogen content 17 to 20%, decomposition temperature is higher than 270 ℃, and 25 ℃, 10% suspension viscosity are not more than 50, the polymerization degree 〉=2500.
Further scheme is: described polynite is organic modification montmonrillonite or sodium-based montmorillonite.
Further scheme is: described organic modification montmonrillonite is a kind of montmorillonite organic derivative, and apparent density is 0.25 to 0.35g/cm 3, average wafer thickness is less than 25nm, and smectite content is greater than 95%, radius-thickness ratio 200.
Further scheme is: described antioxidant is an antioxidant 168.
The present invention also provides the preparation method of described low density polyethylene fire retardant matrix material, adopts following steps:
(1) nylon 6, linear low density polyethylene, new LDPE (film grade) are connect maleic anhydride, polynite is added in the homogenizer, mixes 2 to 10 minutes, will mix material and be discharged into twin screw extruder and extrude;
(2) melamine coated ammonium polyphosphate, tetramethylolmethane are mixed by weight;
(3) with the mixing of materials of step (1), (2), and add antioxidant, utilize the twin screw extruder extruding pelletization, oven dry promptly makes the low density polyethylene fire retardant matrix material.
Wherein, each section of twin screw extruder temperature is as shown in the table
Each section of table 1 twin screw temperature
Figure BDA0000034263410000031
Annotate: feeding: 7Hz; Engine speed: 240r/min.
Among the present invention, the matrix of flame-proof composite material is a linear low density polyethylene, nontoxic, tasteless, odorless, compare with new LDPE (film grade) commonly used, have higher softening temperature and melt temperature, advantages such as intensity is big, good toughness, rigidity is big, heat-resisting, winter hardiness is good are arranged, also have good environmental stress crack resistance, performance such as impact strength, tear-resistant intensity, but and acid-and base-resisting, organic solvent; New LDPE (film grade) connects a maleic anhydride as solubilizing agent, is used to improve the consistency of fire retardant and resin; The melamine coated ammonium polyphosphate provides source of the gas and acid source in the expandable flame retardant system, make the polyethylene dehydration carbonization during burning, forms the very low non-volatile coke of thermal conduction; The gas inflation coke layer that produces plays intercepting O 2And heat passage effect; Tetramethylolmethane makes surperficial charcoal layer fine and close more as the neat coal amout of charcoal source increase PE.Three's synergy improves flame retardant effect.Polynite and nylon 6 improve flame retardant effect as synergistic flame retardant; Antioxidant is phenols or Phosphorus antioxidant.
The flame-proof composite material of the present invention preparation, combustion fumes is little, and molten drop is few, and the fire retardant addition is low, excellent thermal stability, material mechanical performance is good, and the flame retarding efficiency height can satisfy the needs of practical application
Embodiment
Embodiment 1
A kind of low density polyethylene fire retardant matrix material, form by following component by weight:
Linear low density polyethylene: 80 parts;
New LDPE (film grade) connects 20 parts of maleic anhydrides;
20 parts of melamine coated ammonium polyphosphates (MAPP);
10 parts of tetramethylolmethanes (PER);
3 parts of organic modification montmonrillonites (OMMT);
Nylon 6 (PA6) is 100 parts;
168 2 parts of antioxidants.
And adopt following preparation method:
(1) nylon 6, linear low density polyethylene, new LDPE (film grade) are connect maleic anhydride, organic modification montmonrillonite is added in the homogenizer, mixes 5 minutes, will mix material and be discharged into twin screw extruder and extrude;
(2) melamine coated ammonium polyphosphate, tetramethylolmethane are mixed by weight;
(3) with the mixing of materials of step (1), (2), and add antioxidant 168, utilize the twin screw extruder extruding pelletization, oven dry promptly makes the low density polyethylene fire retardant matrix material.
Embodiment 2
A kind of low density polyethylene fire retardant matrix material, form by following component by weight:
Linear low density polyethylene: 80 parts;
New LDPE (film grade) connects 20 parts of maleic anhydrides;
20 parts of melamine coated ammonium polyphosphates (MAPP);
10 parts of tetramethylolmethanes (PER);
4 parts of sodium-based montmorillonites (Na-MMT);
Nylon 6 (PA6) is 95 parts;
168 2 parts of antioxidants.
And adopt following preparation method:
(1) nylon 6, linear low density polyethylene, new LDPE (film grade) are connect maleic anhydride, sodium-based montmorillonite is added in the homogenizer, mixes 10 minutes, will mix material and be discharged into twin screw extruder and extrude;
(2) melamine coated ammonium polyphosphate, tetramethylolmethane are mixed by weight;
(3) with the mixing of materials of step (1), (2), and add antioxidant 168, utilize the twin screw extruder extruding pelletization, oven dry promptly makes the low density polyethylene fire retardant matrix material.
The flame-proof composite material performance test such as the following table of embodiment 1,2 preparations:
Test event Unit Embodiment 1 Embodiment 2
Oxygen index ---- 33.4 30.2
Loss on ignition ％ 27.5 25.5
Tensile strength MPa 9.6 8.3
Elongation at break ％ 515.8 271.4
Notched Izod impact strength KJ/m 2 24.7 16.9

Claims (8)

1. low density polyethylene fire retardant matrix material, it is characterized in that: described material is made up of following component by weight:
Linear low density polyethylene: 70 to 90 parts; New LDPE (film grade) connects 10 to 20 parts of maleic anhydrides; 10 to 30 parts of melamine coated ammonium polyphosphates; 5 to 15 parts of tetramethylolmethanes; 1 to 5 part of polynite; 6 60 to 100 parts of nylon, 1 to 4 part of antioxidant.
2. low density polyethylene fire retardant matrix material according to claim 1 is characterized in that: the density 0.915 of described linear low density polyethylene is to 0.930g/cm 3, melting index is not more than 2.5g/10min under 190 ℃, 2.16kg condition, and tensile yield strength is not less than 2.5MPa under the 50mm/min condition, and elongation at break is not less than 500% under the 50mm/min condition, and tensile break stress is not less than 12MPa.
3. low density polyethylene fire retardant matrix material according to claim 1 is characterized in that: described new LDPE (film grade) meets the density 0.93g/cm of a maleic anhydride 3, melting index 0.8 is to 3.0g/10min under 190 ℃, 2.16kg condition, and 110 ℃ of Vicat softening points, the percentage of grafting of determination of acid-basetitration are 0.85%.
4. low density polyethylene fire retardant matrix material according to claim 1 is characterized in that: the density 1.8g/cm of described melamine coated ammonium polyphosphate 3To 2.0g/cm 3, phosphorus content 28 to 30%, nitrogen content 17 to 20%, decomposition temperature is higher than 270 ℃, and 25 ℃, 10% suspension viscosity are not more than 50, the polymerization degree 〉=2500.
5. low density polyethylene fire retardant matrix material according to claim 1 is characterized in that: described polynite is organic modification montmonrillonite or sodium-based montmorillonite.
6. low density polyethylene fire retardant matrix material according to claim 5 is characterized in that: described organic modification montmonrillonite is a kind of montmorillonite organic derivative, and apparent density is 0.25 to 0.35g/cm 3, average wafer thickness is less than 25nm, and smectite content is greater than 95%, radius-thickness ratio 200.
7. the preparation method of the described low density polyethylene fire retardant matrix material of the arbitrary claim of claim 1 to 6 is characterized in that adopting following steps:
(1) nylon 6, linear low density polyethylene, new LDPE (film grade) are connect maleic anhydride, polynite is added in the homogenizer, mixes 2 to 10 minutes, will mix material and be discharged into twin screw extruder and extrude;
(2) melamine coated ammonium polyphosphate, tetramethylolmethane are mixed by weight;
(3) with the mixing of materials of step (1), (2), and add antioxidant, utilize the twin screw extruder extruding pelletization, oven dry promptly makes the low density polyethylene fire retardant matrix material.
8. the preparation method of low density polyethylene fire retardant matrix material according to claim 7 is characterized in that each section of twin screw extruder temperature is: I section, 160 ℃; The II section, 175 ℃; The III section, 190 ℃; The IV section, 200 ℃; The V section, 205 ℃; The VI section, 210 ℃; The VII section, 205 ℃; The VIII section, 200 ℃; The IX section, 195 ℃; Head, 185 ℃.
CN2010105590859A 2010-11-25 2010-11-25 LDPE flame retardant composite material and preparation method thereof Expired - Fee Related CN102050987B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993861A (en) * 2012-09-29 2013-03-27 北京东方雨虹防水技术股份有限公司 Flame-retardant acrylic acid veneer coating and preparation method thereof
CN103435885A (en) * 2013-08-14 2013-12-11 吴江市英力达塑料包装有限公司 Degradable inflaming retarding air bubble film and preparation method thereof
CN104774450A (en) * 2015-04-22 2015-07-15 合肥康龄养生科技有限公司 Novel antimicrobial nylon composite material and preparation method thereof
CN107189151A (en) * 2017-03-30 2017-09-22 扬州众成纳米科技有限公司 A kind of preparation method of flame-retardant modified polyethylene

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CN1587308A (en) * 2004-08-06 2005-03-02 华南理工大学 Process for preparing polyolefine/montmorillonite nano non-halogen flame-resisting material
US20070228343A1 (en) * 2004-05-13 2007-10-04 Michael Roth Flame Retardants
CN101205325A (en) * 2006-12-20 2008-06-25 上海日之升新技术发展有限公司 Preparation of low-smoke halogen-free flame-retardant electric wire and cable material
CN101280083A (en) * 2007-04-06 2008-10-08 湖南科天新材料有限公司 Halogen-free flame-retardant polyethylene functional material for aluminum-plastic composite board and preparation thereof
CN101407605A (en) * 2008-11-26 2009-04-15 东北林业大学 Expansion flame-retardant material of polyethylene and copolymer thereof

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CN101205325A (en) * 2006-12-20 2008-06-25 上海日之升新技术发展有限公司 Preparation of low-smoke halogen-free flame-retardant electric wire and cable material
CN101280083A (en) * 2007-04-06 2008-10-08 湖南科天新材料有限公司 Halogen-free flame-retardant polyethylene functional material for aluminum-plastic composite board and preparation thereof
CN101407605A (en) * 2008-11-26 2009-04-15 东北林业大学 Expansion flame-retardant material of polyethylene and copolymer thereof

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Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993861A (en) * 2012-09-29 2013-03-27 北京东方雨虹防水技术股份有限公司 Flame-retardant acrylic acid veneer coating and preparation method thereof
CN103435885A (en) * 2013-08-14 2013-12-11 吴江市英力达塑料包装有限公司 Degradable inflaming retarding air bubble film and preparation method thereof
CN104774450A (en) * 2015-04-22 2015-07-15 合肥康龄养生科技有限公司 Novel antimicrobial nylon composite material and preparation method thereof
CN107189151A (en) * 2017-03-30 2017-09-22 扬州众成纳米科技有限公司 A kind of preparation method of flame-retardant modified polyethylene

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