CN109320843A - Polypropylene flame redardant thermal insulation material and preparation method thereof - Google Patents

Polypropylene flame redardant thermal insulation material and preparation method thereof Download PDF

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Publication number
CN109320843A
CN109320843A CN201811185261.XA CN201811185261A CN109320843A CN 109320843 A CN109320843 A CN 109320843A CN 201811185261 A CN201811185261 A CN 201811185261A CN 109320843 A CN109320843 A CN 109320843A
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thermal insulation
hollow glass
parts
insulation material
glass micropearl
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汪琦
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Anqing Zye New Material Technology Extension Service Co Ltd
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Anqing Zye New Material Technology Extension Service Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/14Copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention proposes a kind of polypropylene flame redardant thermal insulation materials and preparation method thereof, including following components: 55~65 parts of acrylic resin, modified 25~35 parts of hollow glass micropearl, 5~10 parts of magnalium hydrotalcite, 1~3 part of phosphomolybdic acid, 1~3 part of titanate coupling agent, 6~12 parts of toughener, 0.2~0.8 part of antioxidant and 0.6~1.8 part of lubricant;Modified hollow glass micropearl is mainly prepared by hollow glass micropearl, maleic anhydride, acrylic acid and benzoyl peroxide.Preparation method: 1) first modified glass microspheres, titanate coupling agent, the acrylic resin that accounts for gross mass 30~40% and the toughener that accounts for gross mass 10~20% are uniformly mixed, go out machine with mixer and prepares master batch;2) master batch that step 1) obtains is mixed with remaining components, through dispersing in double screw extruder in 200~240 DEG C of melting mixings, extruding pelletization.The thermal coefficient of the thermal insulation material is low, thermal insulation property and excellent fireproof performance.

Description

Polypropylene flame redardant thermal insulation material and preparation method thereof
Technical field
The invention belongs to plastics arts, and in particular to a kind of polypropylene flame redardant thermal insulation material and preparation method thereof.
Background technique
Polypropylene enters each corner of daily life as a kind of general-purpose plastics, by the modified polypropylene of miberal powder Material relies on its good rigidity, lower shrinking percentage and deformation, has obtained extensive utilization on household appliances.It is currently used More methods is that elastomeric material is added in polypropylene matrix to improve impact strength, by introducing 10-40% talcum powder, cloud The fillers such as female powder, wollastonite, kaolin improve tensile strength, bending strength and bending modulus, by introducing damage resistant agent such as Silicone master batch, amide containing resinoid improve scratch resistant performance.
Halogenated flame retardant is one of maximum organic fire-retardant of yield in the world at present, it is with the factors such as flame retardant effect is significant It is widely applied in polyolefin flame-retardant.It is domestic at present mainly to use organohalogen compounds and antimony oxide (Sb2O3) be used in compounding Flame retardant effect is improved to generate synergistic effect, the mechanism of action is the SbX generated when burning3It can effectively capture material burning production Raw free radical and terminate radical chain reaction.Common V-0 polypropylene flame redardant domestic at present, the proportion of fire retardant are 21 part ten Bromine diphenylethane and 7 parts of Sb2O3Compounding, but since antimony oxide price rises steadily and other composite factors, the preparation of this method Polypropylene flame redardant cost is excessively high.
Currently, metal delivery tubes are widely used in oil exploitation, oil transportation, natural gas transportation, city heat supply, city The every field such as water supply.Due to the difference of pumped (conveying) medium and transport environment, people need to take metallic conduit different protections Measure, it is such as heat-resisting;Anticorrosion;Scratch resistance etc..In addition, during conveying high-temperature medium, it can also require that reducing entire defeated The thermal coefficient for sending pipeline guarantees the temperature of pumped (conveying) medium.For example, to will lead to oil product viscous for the reduction of oil product temperature in oil pipeline Degree increases to reduce transfer efficiency, more seriously, the wax contained in oil product is made to be precipitated and block conveyance conduit sometimes.And In the transmission process of hot water and steam, if not reducing the thermal coefficient of metal delivery tubes, the consumption of the energy can be increased, is increased Unnecessary expenditures.Therefore, in order to improve the effect that metal tube conveys, people can take a variety of safeguard measures.
Currently, the thermal insulation material that metal delivery tubes use has waterglass perlite shell, glass wool rigid section, polyurethane foam Plastics etc..Since Plastic thermal insulation material has many advantages, such as that density is low, easy to process is increasingly being applied to middle low temperature (no Higher than 140 DEG C) heat preservation of conveyance conduit.Chinese patent CN103819644A discloses a kind of " pipe insulation material of good fluidity Material and preparation method thereof ", the pipe insulation material is polyurethane foam plastics, though thermal insulation property is excellent, its intensity mistake Low, water resistance has deficiency, is not suitable for the heat preservation of buried pipeline and submarine pipeline;In addition, preparing polyurethane foam plastics guarantor Warm layer needs prefabricated mould, causes engineering construction efficiency relatively low.
Summary of the invention
The present invention proposes a kind of polypropylene flame redardant thermal insulation material, and the thermal coefficient of the thermal insulation material is low, thermal insulation property and resistance Combustion is had excellent performance.
The technical scheme of the present invention is realized as follows:
A kind of polypropylene flame redardant thermal insulation material, according to the number of parts by weight, including following components:
55~65 parts of acrylic resin, modified 25~35 parts of hollow glass micropearl, 5~10 parts of magnalium hydrotalcite, phosphomolybdic acid 1 ~3 parts, 1~3 part of titanate coupling agent, 6~12 parts of toughener, 0.2~0.8 part of antioxidant and 0.6~1.8 part of lubricant;Institute Modified hollow glass micropearl is stated mainly to be prepared by hollow glass micropearl, maleic anhydride, acrylic acid and benzoyl peroxide.
Preferably, the modified glass microspheres preparation method the following steps are included:
1) hollow glass micropearl is dissolved in saturation ammonia spirit, at ultrasonic agitation 3~6 hours, by hollow glass after stirring Glass microballon filters out, and cleans drying;
2) hollow glass micropearl after drying is put into the aqueous solution of acrylic acid, adds maleic anhydride and peroxidating Benzoyl is stirred to react 4~8 hours, is filtered, and drying can be obtained modified glass microspheres.
Preferably, the partial size of the hollow glass micropearl is 40 μm~100 μm.
Preferably, the mass ratio of the hollow glass micropearl and the acrylic acid is 10~16:1, the hollow glass The mass ratio of microballon and the maleic anhydride is 23~28:1, the mass ratio of the acrylic acid and the benzoyl peroxide For 6~12:1.
Preferably, the acrylic resin is one or both of copolymer polypropylene or homopolypropylene.
Preferably, the titanate coupling agent is (the dioctyl phosphoric acid acyloxy) titanate esters of isopropyl three or three different hard esters Sour isopropyl titanate.
Preferably, the toughener is ethylene-octene copolymer, ethylene-alpha-olefin polymers or Ethylene-Propylene-Diene One of copolymer or more than one.
Preferably, the antioxidant is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, Asia One of tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester and the double octadecyls of thio-2 acid are a variety of.
It is a further object to provide a kind of preparation methods of polypropylene flame redardant thermal insulation material, including following step It is rapid:
1) first by modified glass microspheres, titanate coupling agent, the acrylic resin for accounting for gross mass 30~40% and total matter is accounted for The toughener of amount 10~20% is uniformly mixed, and is gone out machine with mixer and is prepared master batch;
2) master batch for obtaining step 1) and magnalium hydrotalcite, phosphomolybdic acid, antioxidant, lubricant, remaining toughener and remaining Lower acrylic resin mixing, through dispersing in double screw extruder in 200~240 DEG C of melting mixings, extruding pelletization.
Beneficial effects of the present invention:
The present invention is mainly prepared by hollow glass micropearl, maleic anhydride, acrylic acid and benzoyl peroxide by selecting To modified hollow glass micropearl, after ultrasonic treatment of the modification hollow glass micropearl by saturation ammonium hydroxide, then with maleic anhydride, third Olefin(e) acid and benzoyl peroxide carry out surface modification treatment, substantially increase the compatible of hollow glass micropearl and acrylic resin Property, so that the filling rate of hollow glass micropearl is improved, so that the polypropylene flame redardant thermal insulation material being prepared is more traditional Polyurethane material thermal coefficient it is lower, while there is good water resistance.The present invention uses magnalium hydrotalcite and phosphomolybdic acid As fire retardant, flame retardant effect is improved, composite material obtained can be not necessarily to bromide fire retardant while guaranteeing that V-0 is fire-retardant With the participation of fire retarding synergist antimony oxide.
Specific embodiment
Embodiment 1
The preparation methods of modified glass microspheres the following steps are included:
1) hollow glass micropearl is dissolved in saturation ammonia spirit, it is after stirring that hollow glass is micro- at ultrasonic agitation 3 hours Pearl filters out, and cleans drying;The partial size of hollow glass micropearl is 40 μm~100 μm.
2) hollow glass micropearl after drying is put into the aqueous solution of acrylic acid, adds maleic anhydride and peroxidating Benzoyl is stirred to react 8 hours, is filtered, and drying can be obtained modified glass microspheres.The matter of hollow glass micropearl and acrylic acid The ratio between amount is 10:1, and the mass ratio of hollow glass micropearl and maleic anhydride is 28:1, the matter of acrylic acid and benzoyl peroxide The ratio between amount is 6:1.
Embodiment 2
The preparation methods of modified glass microspheres the following steps are included:
1) hollow glass micropearl is dissolved in saturation ammonia spirit, it is after stirring that hollow glass is micro- at ultrasonic agitation 6 hours Pearl filters out, and cleans drying;The partial size of hollow glass micropearl is 40 μm~100 μm.
2) hollow glass micropearl after drying is put into the aqueous solution of acrylic acid, adds maleic anhydride and peroxidating Benzoyl is stirred to react 4 hours, is filtered, and drying can be obtained modified glass microspheres.
The mass ratio of hollow glass micropearl and the acrylic acid is 16:1, the hollow glass micropearl and the maleic acid The mass ratio of acid anhydride is 23:1, and the mass ratio of the acrylic acid and the benzoyl peroxide is 12:1.
Embodiment 3
A kind of polypropylene flame redardant thermal insulation material, according to the number of parts by weight, including following components:
61 parts of acrylic resin, embodiment 12 parts of 7 parts of 30 parts of modification hollow glass micropearl, magnalium hydrotalcite, phosphomolybdic acid, Isopropyl three (dioctyl phosphoric acid acyloxy) 2 parts of titanate esters, 8 parts of ethylene-octene copolymer, (2, the 4- di-t-butyls of phosphorous acid three Phenyl) 0.6 part of ester and 1.2 parts of polyethylene wax.
Preparation method:
1) first by the modification hollow glass micropearl of embodiment 1, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, account for it is total The copolymer polypropylene of quality 35% and the ethylene-octene copolymer for accounting for gross mass 15% are uniformly mixed, and go out machine preparation with mixer Master batch;
2) master batch for obtaining step 1) and magnalium hydrotalcite, phosphomolybdic acid, phosphorous acid three (2,4- di-tert-butyl-phenyl) ester, Polyethylene wax, remaining ethylene-octene copolymer and remaining copolymer polypropylene mixing, through in double screw extruder at 200~240 DEG C Melting mixing dispersion, extruding pelletization.
Embodiment 4
A kind of polypropylene flame redardant thermal insulation material, according to the number of parts by weight, including following components:
10 parts of 25 parts of modification hollow glass micropearl, magnalium hydrotalcite, the phosphomolybdic acid 1 of 55 parts of acrylic resin, embodiment 2 Part, 1 part of three iso stearate isopropyl titanate, 6 parts of ethylene-alpha-olefin polymers, four [β-(3,5- di-t-butyl -4- hydroxy benzenes Base) propionic acid] 0.2 part of pentaerythritol ester and 0.6 part of polypropylene wax.
Preparation method:
1) first by the modification hollow glass micropearl of embodiment 2, three iso stearate isopropyl titanates, account for the equal of gross mass 30% Poly- polypropylene and the ethylene-alpha-olefin polymers for accounting for gross mass 20% are uniformly mixed, and are gone out machine with mixer and are prepared master batch;
2) master batch for obtaining step 1) and magnalium hydrotalcite, phosphomolybdic acid, four [β-(3,5- di-t-butyl -4- hydroxy benzenes Base) propionic acid] pentaerythritol ester, polypropylene wax, remaining ethylene-alpha-olefin polymers and remaining homopolypropylene rouge mixing, through double Disperse in screw extruder in 200~240 DEG C of melting mixings, extruding pelletization.
Embodiment 5
A kind of polypropylene flame redardant thermal insulation material, according to the number of parts by weight, including following components:
30 parts of copolymer polypropylene, 35 parts of homopolypropylene, 35 parts of the modification hollow glass micropearl of embodiment 1, magnalium neatly 5 parts of stone, 3 parts of phosphomolybdic acid, isopropyl three (dioctyl phosphoric acid acyloxy) 3 parts of titanate esters, 6 parts of ethylene-octene copolymer, thio two Double 0.8 part and 1.8 parts of polyethylene wax of the octadecyls of propionic acid.
Preparation method:
1) first by the modification hollow glass micropearl of embodiment 1, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, account for it is total The acrylic resin of quality 40% and the ethylene-octene copolymer for accounting for gross mass 10% are uniformly mixed, and go out machine preparation with mixer Master batch;
2) master batch for obtaining step 1) and magnalium hydrotalcite, phosphomolybdic acid, thio-2 acid double octadecyls, polyethylene Wax, remaining ethylene-octene copolymer and remaining acrylic resin mixing, through mixed in 200~240 DEG C of meltings in double screw extruder Close dispersion, extruding pelletization.
Comparative example 1
A kind of polypropylene flame redardant thermal insulation material, according to the number of parts by weight, including following components:
61 parts of acrylic resin, 30 parts of hollow glass micropearl, 7 parts of magnalium hydrotalcite, 2 parts of phosphomolybdic acid, (two is pungent for isopropyl three Base phosphoric acid acyloxy) 2 parts of titanate esters, 8 parts of ethylene-octene copolymer, 0.6 part of phosphorous acid three (2,4- di-tert-butyl-phenyl) ester and 1.2 parts of polyethylene wax.
It is substantially the same manner as Example 1, the difference is that each component and content.
Test example
The polypropylene flame redardant thermal insulation material of embodiment 3-5, comparative example 1 is tested for the property, tensile strength testing standard Foundation ISO 527-2, test condition: 23 DEG C of temperature, rate of extension 50mm/min;Bending strength testing standard foundation ISO 178, Test condition: 23 DEG C of temperature, rate 2mm/min, span 64mm are bent;Notch impact strength testing standard is according to ISO 179- 1eA, test condition: 23 DEG C of temperature;Thermal coefficient, ASTMC518,23 DEG C.Measurement result is shown in Table 1.
Table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of polypropylene flame redardant thermal insulation material, which is characterized in that according to the number of parts by weight, including following components:
55~65 parts of acrylic resin, modified 25~35 parts of hollow glass micropearl, 5~10 parts of magnalium hydrotalcite, phosphomolybdic acid 1~3 Part, 1~3 part of titanate coupling agent, 6~12 parts of toughener, 0.2~0.8 part of antioxidant and 0.6~1.8 part of lubricant;It is described to change Property hollow glass micropearl is mainly prepared by hollow glass micropearl, maleic anhydride, acrylic acid and benzoyl peroxide.
2. polypropylene flame redardant thermal insulation material according to claim 1, which is characterized in that the preparation of the modified glass microspheres Method the following steps are included:
1) hollow glass micropearl is dissolved in saturation ammonia spirit, it is after stirring that hollow glass is micro- at ultrasonic agitation 3~6 hours Pearl filters out, and cleans drying;
2) hollow glass micropearl after drying is put into the aqueous solution of acrylic acid, adds maleic anhydride and benzoyl peroxide first Acyl is stirred to react 4~8 hours, is filtered, and drying can be obtained modified glass microspheres.
3. polypropylene flame redardant thermal insulation material according to claim 2, which is characterized in that the partial size of the hollow glass micropearl It is 40 μm~100 μm.
4. polypropylene flame redardant thermal insulation material according to claim 2, which is characterized in that the hollow glass micropearl with it is described The mass ratio of acrylic acid is 10~16:1, and the mass ratio of the hollow glass micropearl and the maleic anhydride is 23~28: 1, the mass ratio of the acrylic acid and the benzoyl peroxide is 6~12:1.
5. polypropylene flame redardant thermal insulation material according to claim 1, which is characterized in that the acrylic resin is that copolymerization is poly- One or both of propylene or homopolypropylene.
6. polypropylene flame redardant thermal insulation material according to claim 1, which is characterized in that the titanate coupling agent is isopropyl (the dioctyl phosphoric acid acyloxy) titanate esters of base three or three iso stearate isopropyl titanates.
7. polypropylene flame redardant thermal insulation material according to claim 1, which is characterized in that the toughener is ethylene-octene One of copolymer, ethylene-alpha-olefin polymers or ethylene-propylene-diene copolymer or more than one.
8. polypropylene flame redardant thermal insulation material according to claim 1, which is characterized in that the antioxidant be selected from four [β-(3, 5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, (2, the 4- di-tert-butyl-phenyl) ester of phosphorous acid three and thio dipropyl One of sour double octadecyls are a variety of.
9. the preparation method of the polypropylene flame redardant thermal insulation material as described in claim 1 to 8 any one, which is characterized in that packet Include following steps:
1) first by modified glass microspheres, titanate coupling agent, the acrylic resin for accounting for gross mass 30~40% and gross mass 10 is accounted for ~20% toughener is uniformly mixed, and is gone out machine with mixer and is prepared master batch;
2) master batch for obtaining step 1) and magnalium hydrotalcite, phosphomolybdic acid, antioxidant, lubricant, remaining toughener and remainder are poly- Allyl resin mixing, through dispersing in double screw extruder in 200~240 DEG C of melting mixings, extruding pelletization.
CN201811185261.XA 2018-10-11 2018-10-11 Polypropylene flame redardant thermal insulation material and preparation method thereof Withdrawn CN109320843A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912890A (en) * 2019-03-27 2019-06-21 哈尔滨理工大学 The fire-retardant low dielectric polypropylene material of one kind and preparation method and application
CN116640389A (en) * 2023-06-25 2023-08-25 北京荣邦汇鑫科技有限责任公司 Thermal insulation material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912890A (en) * 2019-03-27 2019-06-21 哈尔滨理工大学 The fire-retardant low dielectric polypropylene material of one kind and preparation method and application
CN116640389A (en) * 2023-06-25 2023-08-25 北京荣邦汇鑫科技有限责任公司 Thermal insulation material and preparation method thereof

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Application publication date: 20190212