CN116554534A - Environment-friendly polypropylene flame-retardant foam material and preparation process thereof - Google Patents

Environment-friendly polypropylene flame-retardant foam material and preparation process thereof Download PDF

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CN116554534A
CN116554534A CN202310806328.1A CN202310806328A CN116554534A CN 116554534 A CN116554534 A CN 116554534A CN 202310806328 A CN202310806328 A CN 202310806328A CN 116554534 A CN116554534 A CN 116554534A
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polypropylene
flame
foam material
retardant
calcium sulfate
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CN116554534B (en
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马沛清
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Kunshan Baming Foam & Plastic Products Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2423/04—Homopolymers or copolymers of ethene
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
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    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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    • C08K7/00—Use of ingredients characterised by shape
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Abstract

The invention relates to the technical field of polymer foaming materials, in particular to an environment-friendly polypropylene flame-retardant foam material and a preparation process thereof, comprising the following steps: extruding polypropylene, ultra-high molecular weight polyethylene, modified polypropylene and an antioxidant through a double-screw extruder, and granulating to obtain master batches; adding calcium sulfate whisker, mixing at high speed for 5-10 min, extruding with a single screw, and injecting carbon dioxide to foam to obtain the foam material. The invention enhances the intermolecular interaction and promotes physical entanglement through the use of the ultra-high molecular weight polyethylene; the calcium sulfate whisker can reduce the energy barrier of cell nucleation and promote the cell nucleation; the modified polypropylene is obtained by reacting maleic anhydride grafted polypropylene with flame-retardant epoxy resin, so that strong system entanglement and crosslinking can be increased, the melt strength is enhanced, and the mechanical property and flame-retardant property of the prepared foam material are improved.

Description

Environment-friendly polypropylene flame-retardant foam material and preparation process thereof
Technical Field
The invention relates to the technical field of polymer foam materials, in particular to an environment-friendly polypropylene flame-retardant foam material and a preparation process thereof.
Background
The polymer foam material is a gas-solid two-phase compound composed of polymer and gas, has the advantages of light weight, good performance such as buffering, adsorption and heat insulation, and is widely applied to various fields of national economy and industry. As one of general plastics, polypropylene has the advantages of high melting point, easy processing, good mechanical property and the like, and compared with polyurethane, polystyrene and polyethylene, the foamed product has better comprehensive performance. Some existing polypropylene foam materials can be foamed by using a chemical foaming agent, and in the foaming process, a great amount of heat can be generated by the decomposition of the organic foaming agent, so that the center of the prepared foam material is carbonized, and formaldehyde can be generated by the decomposition of some of the foam material, so that the foam material is extremely not environment-friendly. And the limiting oxygen index of polypropylene is lower and is about 18, and the prepared foam material is easy to burn, so that potential safety hazard is caused. Therefore, we propose an environment-friendly polypropylene flame-retardant foam material and a preparation process thereof.
Disclosure of Invention
The invention aims to provide an environment-friendly polypropylene flame-retardant foam material and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
extruding polypropylene, ultra-high molecular weight polyethylene, modified polypropylene and an antioxidant through a double-screw extruder, and granulating to obtain master batches;
adding calcium sulfate whisker, mixing at high speed for 5-10 min, extruding with a single screw, and injecting carbon dioxide to foam to obtain the foam material.
Further, the temperatures of the zones of the twin-screw extruder were: 170-175 ℃ in the first area, 180-185 ℃ in the second area, 190-195 ℃ in the third area, 200-205 ℃ in the fourth area, 200-205 ℃ in the extrusion temperature and 90-120 r/min in the screw speed.
Further, the temperature of each zone of the single screw extruder is: 180-185 ℃ in the first area, 200-205 ℃ in the second area, 200-205 ℃ in the third area, 180-185 ℃ in the fourth area, 165-170 ℃ in the fifth area, 155-160 ℃ in the sixth area, 157-159 ℃ in the extrusion temperature, and 40-60 r/min in the screw rotation speed.
Further, the foam material comprises the following components in parts by mass: 80 to 100 parts of polypropylene, 12 to 15 parts of ultra-high molecular weight polyethylene, 10 to 30 parts of modified polypropylene, 0.8 to 1.2 parts of calcium sulfate whisker and 0.2 to 0.5 part of antioxidant.
Polypropylene: T30S, melt flow index 3.2g/10min (230 ℃,2.16 kg), from Zhenhai refining division of China petrochemical Co., ltd;
ultra-high molecular weight polyethylene: 2040, viscosity average molecular weight 3.0X10 6 g/mol, from Shanghai Bile chemical engineering Co., ltd;
calcium sulfate whisker; NP-W008 from Shanghai Pelargonium whisker Co., ltd;
the antioxidant is antioxidant 1010.
Carbon dioxide is a foaming agent, and the injection amount of the carbon dioxide is 10wt% of the mass of the melt; foaming pressure is 10-18 MPa, and foaming temperature is 151-155 ℃;
carbon dioxide: purity 99.9%, from Ningbo Wanli gas Co., ltd;
before the solid materials and the prepared master batch are used, the solid materials and the prepared master batch are placed in a vacuum drying oven at 80 ℃ for drying for 4 hours;
the master batch is a cylinder with the length of 12-15 mm and the diameter of 3-4 mm.
In the technical scheme, the polypropylene is selected as the main resin component of the foam material because the polypropylene has the advantages of no toxicity, environmental protection, higher heat distortion temperature, better room temperature impact, rigidity and other comprehensive properties. The addition of the ultra-high molecular weight polyethylene can solve the problem of poor melt strength of the semi-crystalline plastic of polypropylene, is beneficial to enhancing the melt strength of the foam material during preparation, improves the foaming multiplying power of the foam material and improves the uniformity of foam cells of the prepared foam material. The calcium sulfate whisker is added as a filler, so that interaction exists between the calcium sulfate whisker and macromolecules such as polypropylene, the calcium sulfate whisker and the ultra-high molecular weight polyethylene can cooperate, physical entanglement is promoted, the melt strength is improved, and the foaming behavior is improved; the composite material can be used as heterogeneous nucleating agent to induce beta-crystal nucleation, reduce energy barrier of cell nucleation, promote cell nucleation, remarkably increase foaming ratio of polypropylene, combine structural and performance characteristics of calcium sulfate whisker, and improve comprehensive mechanical properties such as tensile strength, compressive strength and the like of the prepared foam material; in addition, the calcium sulfate whisker is used as a nonmetallic material, has high melting point, good heat resistance and flame retardant capability, and can effectively improve the flame retardant property of the prepared foam material. Compared with chemical foaming phase, carbon dioxide has the characteristics of environmental friendliness and production safety.
Further, the calcium sulfate whisker is subjected to surface modification, and the specific process is as follows:
mixing gamma-glycidoxypropyl trimethoxy silane and methanol, regulating the pH of a system to 7.8-8.2, carrying out hydrolysis reaction at 40-42 ℃ for 100-150 min, adding calcium sulfate whisker, heating to 138-142 ℃ and reacting for 100-150 min to obtain epoxy modified calcium sulfate whisker;
adding amino lignin and phosphoric acid, and reacting for 2-4 h at 30-50 ℃; cooling after the reaction, filtering, washing and drying at 120 ℃ to obtain the modified calcium sulfate whisker.
Further, the mass ratio of the calcium sulfate whisker to the gamma-glycidol ether oxypropyl trimethoxysilane to the amino lignin to the phosphoric acid is 100 (5-8): 60-85): 0.85-1.33;
the ratio of the gamma-glycidoxypropyl trimethoxysilane to the methanol is (1-5) g/100mL.
Further, the amino lignin is prepared by the following process:
mixing deionized water, ethanol and OP-10, stirring for 12-18 min, adding lignin, stirring and mixing for 12-18 min, regulating the pH of a system to 3-4 by using hydrochloric acid, slowly adding 3-aminopropyl dimethyl methoxysilane, and reacting for 12-24 h at 38-42 ℃; centrifuging, taking and washing the precipitate, and drying at 60 ℃ for 12 hours to obtain the amino lignin.
Further, the mass ratio of lignin to 3-aminopropyl dimethyl methoxysilane is 100 (10-20);
the proportion of lignin, deionized water, ethanol and OP-10 is 10g (30-40) mL (90-100) mL (1.0-1.2);
the mass concentration of the hydrochloric acid is 36-38%;
lignin: the alkali lignin has a particle size of 200 meshes and is derived from Jinan Yanghai chemical industry Co.
In the technical scheme, the lignin molecule contains aryl, phenolic hydroxyl, alcoholic hydroxyl and other groups, and can be used as a carbon source in a flame-retardant system. The calcium sulfate whisker is subjected to surface modification, firstly, gamma-glycidyl ether oxypropyl trimethoxy silane (KH 560) is utilized to couple the calcium sulfate whisker, epoxy groups are introduced to the surface of the calcium sulfate whisker, amino lignin is loaded on the surface of the calcium sulfate whisker by utilizing the reaction mechanism between epoxy and amino groups and between amino groups and phosphoric acid, and elements such as nitrogen, silicon, phosphorus and the like are introduced, so that a formed carbon layer is more continuous, compact and complete, heat transfer and smoke release in the combustion process are inhibited, good flame retardant performance is exerted, and the flame retardant and thermal stability of the foam material can be further improved. The modified calcium sulfate whisker can also improve the compatibility between the calcium sulfate whisker and polypropylene, improve the interface strength of the calcium sulfate whisker, and further improve the comprehensive mechanical properties such as the tensile strength, the compressive strength and the like of the prepared foam material.
Further, the modified polypropylene is prepared by the following process:
and (3) taking polypropylene grafted maleic anhydride (PP-g-MAH), flame-retardant epoxy resin, zinc acetylacetonate and antioxidant 1010, and extruding by a single screw at 187-192 ℃ to obtain the modified polypropylene.
Further, the modified polypropylene comprises the following components in parts by mass: 100 parts of polypropylene grafted maleic anhydride (PP-g-MAH), 6-22 parts of flame-retardant epoxy resin, 0.1-0.2 part of catalyst zinc acetylacetonate and 0.5-1.0 part of antioxidant 1010.
Further, the flame-retardant epoxy resin is prepared by the following process:
mixing ethanol and amino lignin, slowly adding 2-thiazolyl propanal, heating to 65-80 ℃ after finishing adding within 30min, and reacting for 5-6 h; DOPO is added, heated to 80-85 ℃ and reacted for 12-13 h; filtering, washing, and drying at 70 ℃ for 12 hours to obtain modified lignin;
and heating the epoxy resin to 130-150 ℃, adding the modified lignin, and stirring for reaction for 30-40 min to obtain the flame-retardant epoxy resin.
Further, the ratio of the amino lignin to the ethanol is (10-12) g/100mL;
the mass ratio of the amino lignin, the 2-thiazolyl propionaldehyde and the DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is 100 (10-21) to 15.5-32.0.
Further, the mass ratio of the epoxy resin to the modified lignin is 100 (10-25).
Maleic anhydride grafted polypropylene (PP-g-MAH): HD900P, from the kyoto science and technology industries, inc;
epoxy resin: e-44, epoxy ester 0.41-0.47 mol/100g, which is from China oil coating chemical industry Co.
In the technical scheme, amino in the amino lignin and aldehyde groups in the 2-thiazolyl propanal are subjected to aldehyde-amine condensation to form aldimine, and the aldimine reacts with DOPO to obtain lignin (modified lignin) with silicon, nitrogen and phosphorus modification; and then blending the obtained modified lignin with epoxy resin, and reacting the ring opening of the epoxy group with an amino group (secondary amino group generated after the addition of aldimine and phosphorus hydrogen bond in DOPO) in the modified lignin to form a long chain. And the epoxy resin with flame retardant property is obtained through the proportion control of the material components. The prepared flame-retardant epoxy resin and maleic anhydride grafted polypropylene are blended at high temperature, and the epoxy resin and anhydride groups are reacted to obtain the modified polypropylene with long chain branches. When the obtained modified polypropylene is melt blended with polypropylene, entanglement points among molecular chain segments can be enhanced, slippage of the chain segments is prevented, the melt strength of the chain segments is enhanced, interface combination among calcium sulfate whisker, polypropylene and ultra-high molecular weight polyethylene can be improved, and the foaming behavior and comprehensive mechanical property of the prepared foam material are improved while the flame retardant property of the foam material is improved.
In the process of blending extrusion of the master batch obtained by co-extrusion of the follow-up polypropylene ultra-high molecular weight polyethylene, the modified polypropylene and the antioxidant with the calcium sulfate whisker, residual epoxy groups in the modified polypropylene are opened to react with amino groups on the surface of the modified calcium sulfate whisker for curing, so that crosslinking points of a system are increased, heat is released in a foaming process, micro bubbles in the system are promoted to expand, and meanwhile, the strength and toughness of a foam hole wall can be enhanced, so that a carbon layer formed in a combustion process is more continuous, compact and complete, and the mechanical property and flame retardant property of the prepared foam material are improved.
Compared with the prior art, the invention has the following beneficial effects:
according to the environment-friendly polypropylene flame-retardant foam material and the preparation process thereof, through the use of the ultra-high molecular weight polyethylene, the intermolecular interaction is enhanced, and the physical entanglement is promoted; the calcium sulfate whisker can reduce the energy barrier of cell nucleation and promote the cell nucleation; the modified polypropylene is obtained by reacting maleic anhydride grafted polypropylene with flame-retardant epoxy resin, so that strong system entanglement and crosslinking can be increased, the melt strength is enhanced, and the mechanical property and flame-retardant property of the prepared foam material are improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the manufacturers of all the raw materials according to the present invention include, without any particular limitation: in the following description of the embodiments of the present invention,
polypropylene: T30S, melt flow index 3.2g/10min (230 ℃,2.16 kg), from Zhenhai refining division of China petrochemical Co., ltd;
ultra-high molecular weight polyethylene: 2040, viscosity average molecular weight 3.0X10 6 g/mol, from Shanghai Bile chemical engineering Co., ltd;
calcium sulfate whisker; NP-W008 from Shanghai Pelargonium whisker Co., ltd;
carbon dioxide: purity 99.9%, from Ningbo Wanli gas Co., ltd;
lignin: the alkali lignin has a particle size of 200 meshes and is derived from Jinan Yanghai chemical industry Co.
Maleic anhydride grafted polypropylene (PP-g-MAH): HD900P, from the kyoto science and technology industries, inc;
epoxy resin: e-44, epoxy ester 0.41-0.47 mol/100g, which is from China oil coating chemical industry Co.
The "parts" described below are all parts by mass, and the mass of the components in the embodiments can be expanded in equal proportions.
Example 1: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
(1) The amino lignin is prepared by the following process:
mixing 30mL of deionized water, 100mL of ethanol and 1.0-gOP-10, stirring for 12min, adding 10g of lignin, stirring and mixing for 12min, regulating the pH of the system to 4 by using 37% hydrochloric acid, slowly adding 1g of 3-aminopropyl dimethyl methoxysilane, and standing at 38 ℃ for reaction for 12h; centrifuging, taking and washing the precipitate, and drying at 60 ℃ for 12 hours to obtain amino lignin;
(2) Preparation of modified calcium sulfate whisker:
mixing 1.0g of gamma-glycidol ether oxypropyl trimethoxy silane and 100mL of methanol, regulating the pH of the system to 7.8, carrying out hydrolysis reaction at 40 ℃ for 100min, adding 20g of calcium sulfate whisker, and heating to 138 ℃ for 100min to obtain epoxy modified calcium sulfate whisker;
adding 12g of amino lignin and 0.17g of phosphoric acid, and reacting for 4 hours at the temperature of 30 ℃; cooling after reaction, suction filtering, washing and drying at 120 ℃ to obtain modified calcium sulfate whisker;
(3) The flame-retardant epoxy resin is prepared by the following process:
mixing 100mL of ethanol and 10g of amino lignin, slowly adding 1.0g of 2-thiazolyl propanal, heating to 65 ℃ after finishing adding within 30min, and reacting for 6h; adding 1.6g DOPO, heating to 80 ℃ and reacting for 13h; filtering, washing, and drying at 70 ℃ for 12 hours to obtain modified lignin;
heating 100g of epoxy resin to 130 ℃, adding 10g of modified lignin, and stirring for reacting for 40min to obtain flame-retardant epoxy resin;
(4) Preparation of modified polypropylene:
100g of polypropylene grafted maleic anhydride (PP-g-MAH), 6g of flame-retardant epoxy resin, 0.1g of zinc acetylacetonate and 0.5g of antioxidant 1010 are taken, and the modified polypropylene is obtained through single screw extrusion at the extrusion temperature of 187 ℃;
(5) Preparation of foam material:
80 parts of polypropylene, 12 parts of ultra-high molecular weight polyethylene, 10 parts of modified polypropylene and 0.2 part of antioxidant 1010 are extruded by a double-screw extruder, and the temperature of each zone of the double-screw extruder is as follows: one region 170 ℃, two regions 180 ℃, three regions 190 ℃, four regions 200 ℃, extrusion temperature 200 ℃, screw rotation speed 90r/min, and granulating to obtain master batch;
adding 0.8 part of modified calcium sulfate whisker, mixing at a high speed for 5min, and extruding by a single screw, wherein the temperature of each region of the single screw extruder is as follows: 180 ℃ in the first area, 200 ℃ in the second area, 200 ℃ in the third area, 180 ℃ in the fourth area, 165 ℃ in the fifth area, 155 ℃ in the sixth area, the extrusion temperature is 157 ℃, the screw speed is 40r/min, and carbon dioxide is injected for foaming, wherein the injection amount of the carbon dioxide is 10wt% of the mass of the melt; the foaming pressure is 10MPa, the foaming temperature is 155 ℃, and the foam material is obtained.
Example 2: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
(1) The amino lignin is prepared by the following process:
mixing 35mL of deionized water, 95mL of ethanol and 1.1-gOP-10, stirring for 15min, adding 10g of lignin, stirring and mixing for 15min, regulating the pH of the system to 3.5 by using 37% hydrochloric acid, slowly adding 1.5g of 3-aminopropyl dimethyl methoxysilane, and reacting at 40 ℃ for 18h; centrifuging, taking and washing the precipitate, and drying at 60 ℃ for 12 hours to obtain amino lignin;
(2) Preparation of modified calcium sulfate whisker:
mixing 1.3g of gamma-glycidol ether oxypropyl trimethoxy silane and 100mL of methanol, regulating the pH of the system to 8.0, carrying out hydrolysis reaction at 41 ℃ for 120min, adding 20g of calcium sulfate whisker, and heating to 140 ℃ for 120min to obtain epoxy modified calcium sulfate whisker;
15g of amino lignin and 0.22g of phosphoric acid are added and reacted for 3 hours at the temperature of 40 ℃; cooling after reaction, suction filtering, washing and drying at 120 ℃ to obtain modified calcium sulfate whisker;
(3) The flame-retardant epoxy resin is prepared by the following process:
mixing 100mL of ethanol and 11g of amino lignin, slowly adding 1.5g of 2-thiazolyl propanal, heating to 72 ℃ after finishing adding within 30min, and reacting for 5.5h; 2.4g DOPO is added, heated to 82 ℃ and reacted for 12.5h; filtering, washing, and drying at 70 ℃ for 12 hours to obtain modified lignin;
taking 100g of epoxy resin, heating to 140 ℃, adding 18g of modified lignin, and stirring for reaction for 35min to obtain flame-retardant epoxy resin;
(4) Preparation of modified polypropylene:
100g of polypropylene grafted maleic anhydride (PP-g-MAH), 14g of flame-retardant epoxy resin, 0.15g of zinc acetylacetonate and 0.8g of antioxidant 1010 are taken, and the modified polypropylene is obtained through single screw extrusion at the extrusion temperature of 190 ℃;
(5) Preparation of foam material:
extruding 90 parts of polypropylene, 14 parts of ultra-high molecular weight polyethylene, 20 parts of modified polypropylene and 0.4 part of antioxidant 1010 through a double-screw extruder, wherein the temperature of each zone of the double-screw extruder is as follows: the first region 172 ℃, the second region 182 ℃, the third region 192 ℃, the fourth region 202 ℃, the extrusion temperature 202 ℃, the screw rotation speed 100r/min, and the master batch is obtained by pelleting;
adding 1.0 part of modified calcium sulfate whisker, mixing at a high speed for 8min, and extruding by a single screw, wherein the temperature of each zone of the single screw extruder is as follows: first region 182 ℃, second region 202 ℃, third region 202 ℃, fourth region 182 ℃, fifth region 168 ℃, sixth region 158 ℃, extrusion temperature 158 ℃, screw speed 50r/min, and carbon dioxide injection for foaming, wherein the carbon dioxide injection amount is 10wt% of the mass of the melt; the foaming pressure is 15MPa, the foaming temperature is 153 ℃, and the foam material is obtained.
Example 3: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
(1) The amino lignin is prepared by the following process:
mixing 40mL of deionized water, 90mL of ethanol and 1.2-gOP-10, stirring for 18min, adding 10g of lignin, stirring and mixing for 18min, regulating the pH of the system to 3 by using 37% hydrochloric acid, slowly adding 2g of 3-aminopropyl dimethyl methoxysilane, and standing at 42 ℃ for reaction for 24h; centrifuging, taking and washing the precipitate, and drying at 60 ℃ for 12 hours to obtain amino lignin;
(2) Preparation of modified calcium sulfate whisker:
mixing 1.6g of gamma-glycidol ether oxypropyl trimethoxy silane and 100mL of methanol, regulating the pH of the system to 8.2, carrying out hydrolysis reaction at 42 ℃ for 150min, adding 20g of calcium sulfate whisker, and heating to 142 ℃ for reaction for 150min to obtain epoxy modified calcium sulfate whisker;
17g of amino lignin and 0.26g of phosphoric acid are added and reacted for 2 hours at 50 ℃; cooling after reaction, suction filtering, washing and drying at 120 ℃ to obtain modified calcium sulfate whisker;
(3) The flame-retardant epoxy resin is prepared by the following process:
mixing 100mL of ethanol and 12g of amino lignin, slowly adding 2.1g of 2-thiazolyl propanal, heating to 80 ℃ after finishing adding within 30min, and reacting for 5h; 3.2g DOPO is added, heated to 85 ℃ and reacted for 12 hours; filtering, washing, and drying at 70 ℃ for 12 hours to obtain modified lignin;
taking 100g of epoxy resin, heating to 150 ℃, adding 25g of modified lignin, and stirring for reaction for 30min to obtain flame-retardant epoxy resin;
(4) Preparation of modified polypropylene:
100g of polypropylene grafted maleic anhydride (PP-g-MAH), 22g of flame-retardant epoxy resin, 0.2g of zinc acetylacetonate and 1.0g of antioxidant 1010 are taken, and the modified polypropylene is obtained through single screw extrusion at the extrusion temperature of 192 ℃;
(5) Preparation of foam material:
100 parts of polypropylene, 15 parts of ultra-high molecular weight polyethylene, 30 parts of modified polypropylene and 0.5 part of antioxidant 1010 are extruded by a double-screw extruder, and the temperature of each zone of the double-screw extruder is as follows: first 175 ℃, second 185 ℃, third 195 ℃, fourth 205 ℃, extrusion temperature 205 ℃, screw rotation speed 120r/min, granulating to obtain master batch;
adding 1.2 parts of modified calcium sulfate whisker, mixing at high speed for 10min, and extruding by a single screw, wherein the temperature of each zone of the single screw extruder is as follows: 185 ℃ in the first area, 205 ℃ in the third area, 205 ℃ in the fourth area, 185 ℃ in the fifth area, 170 ℃ in the sixth area, 160 ℃ in the extrusion temperature 159 ℃, the rotating speed of the screw is 60r/min, and simultaneously carbon dioxide is injected for foaming, wherein the injection amount of the carbon dioxide is 10wt% of the mass of the melt; foaming pressure is 18MPa, foaming temperature is 151 ℃, and foam material is obtained.
Comparative example 1: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
(1) The amino lignin is prepared by the following process:
mixing 30mL of deionized water, 100mL of ethanol and 1.0-gOP-10, stirring for 12min, adding 10g of lignin, stirring and mixing for 12min, regulating the pH of the system to 4 by using 37% hydrochloric acid, slowly adding 1g of 3-aminopropyl dimethyl methoxysilane, and standing at 38 ℃ for reaction for 12h; centrifuging, taking and washing the precipitate, and drying at 60 ℃ for 12 hours to obtain amino lignin;
(2) Preparation of modified calcium sulfate whisker:
mixing 1.0g of gamma-aminopropyl triethoxysilane and 100mL of methanol, regulating the pH of the system to 7.8, carrying out hydrolysis reaction at 40 ℃ for 100min, adding 20g of calcium sulfate whisker, and heating to 138 ℃ for reaction for 100min to obtain modified calcium sulfate whisker;
(3) The flame-retardant epoxy resin is prepared by the following process:
mixing 100mL of ethanol and 10g of amino lignin, slowly adding 1.0g of 2-thiazolyl propanal, heating to 65 ℃ after finishing adding within 30min, and reacting for 6h; adding 1.6g DOPO, heating to 80 ℃ and reacting for 13h; filtering, washing, and drying at 70 ℃ for 12 hours to obtain modified lignin;
heating 100g of epoxy resin to 130 ℃, adding 10g of modified lignin, and stirring for reacting for 40min to obtain flame-retardant epoxy resin;
(4) Preparation of modified polypropylene:
100g of polypropylene grafted maleic anhydride (PP-g-MAH), 6g of flame-retardant epoxy resin, 0.1g of zinc acetylacetonate and 0.5g of antioxidant 1010 are taken, and the modified polypropylene is obtained through single screw extrusion at the extrusion temperature of 187 ℃;
step (5) was the same as in example 1 to obtain a foam.
Comparative example 2: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
(1) Preparation of modified calcium sulfate whisker:
mixing 1.0g of gamma-aminopropyl triethoxysilane and 100mL of methanol, regulating the pH of the system to 7.8, carrying out hydrolysis reaction at 40 ℃ for 100min, adding 20g of calcium sulfate whisker, and heating to 138 ℃ for reaction for 100min to obtain modified calcium sulfate whisker;
(2) The flame-retardant epoxy resin is prepared by the following process:
heating 100g of epoxy resin to 130 ℃, adding 10g of lignin, and stirring for reacting for 40min to obtain flame-retardant epoxy resin;
(3) Preparation of modified polypropylene:
100g of polypropylene grafted maleic anhydride (PP-g-MAH), 6g of flame-retardant epoxy resin, 0.1g of zinc acetylacetonate and 0.5g of antioxidant 1010 are taken, and the modified polypropylene is obtained through single screw extrusion at the extrusion temperature of 187 ℃;
step (4) was the same as step (5) in example 1, to obtain a foam.
Comparative example 3: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
(1) Preparation of modified calcium sulfate whisker:
mixing 1.0g of gamma-aminopropyl triethoxysilane and 100mL of methanol, regulating the pH of the system to 7.8, carrying out hydrolysis reaction at 40 ℃ for 100min, adding 20g of calcium sulfate whisker, and heating to 138 ℃ for reaction for 100min to obtain modified calcium sulfate whisker;
(2) Preparation of modified polypropylene:
100g of polypropylene grafted maleic anhydride (PP-g-MAH), 6g of epoxy resin, 0.1g of zinc acetylacetonate and 0.5g of antioxidant 1010 are taken, and the modified polypropylene is obtained through single screw extrusion at the extrusion temperature of 187 ℃;
step (3) was the same as step (5) in example 1, to obtain a foam.
Comparative example 4: the preparation process of the environment-friendly polypropylene flame-retardant foam material comprises the following steps:
(1) Preparation of modified calcium sulfate whisker:
mixing 1.0g of gamma-aminopropyl triethoxysilane and 100mL of methanol, regulating the pH of the system to 7.8, carrying out hydrolysis reaction at 40 ℃ for 100min, adding 20g of calcium sulfate whisker, and heating to 138 ℃ for reaction for 100min to obtain modified calcium sulfate whisker;
(2) Preparation of foam material:
80 parts of polypropylene, 12 parts of ultra-high molecular weight polyethylene, 10 parts of polypropylene grafted maleic anhydride and 0.2 part of antioxidant 1010 are extruded by a double-screw extruder, and the temperature of each zone of the double-screw extruder is as follows: one region 170 ℃, two regions 180 ℃, three regions 190 ℃, four regions 200 ℃, extrusion temperature 200 ℃, screw rotation speed 90r/min, and granulating to obtain master batch;
adding 0.8 part of modified calcium sulfate whisker, mixing at a high speed for 5min, and extruding by a single screw, wherein the temperature of each region of the single screw extruder is as follows: 180 ℃ in the first area, 200 ℃ in the second area, 200 ℃ in the third area, 180 ℃ in the fourth area, 165 ℃ in the fifth area, 155 ℃ in the sixth area, the extrusion temperature is 157 ℃, the screw speed is 40r/min, and carbon dioxide is injected for foaming, wherein the injection amount of the carbon dioxide is 10wt% of the mass of the melt; the foaming pressure is 10MPa, the foaming temperature is 155 ℃, and the foam material is obtained.
Experiment: the foam materials obtained in examples 1 to 3 and comparative examples 1 to 4 were sampled, and the properties thereof were examined and the results were recorded, respectively:
tensile strength test: using GB/T13022 as a reference standard, adopting an electronic tensile machine to test the tensile property of a foam material sample, wherein the sample is dumbbell-shaped, the size is 50mm multiplied by 6mm multiplied by 4mm, and the tensile rate is 1mm/min;
compression strength test: testing the compression performance of a foam material sample by adopting a universal electronic tester, wherein the sample size is phi 11mm multiplied by 11mm; in the test, the maximum pressing amount of the sample is 60% of the height of the sample, and the compression rate is 1mm/min;
flame retardant performance test: foam samples were tested for limiting oxygen index using GB/T2406 as a reference standard.
From the data in the above table, the following conclusions can be clearly drawn:
the foams obtained in examples 1-3 were compared with the foams obtained in comparative examples 1-4, and it was found that,
the foams obtained in examples 1-3 have higher tensile strength, compressive strength and limiting oxygen index data than the comparative examples, which fully demonstrates that the present invention achieves improvements in mechanical properties and flame retardant properties of the foams produced.
Compared with the example 1, the modified calcium sulfate whisker in the comparative example 1 is gamma-aminopropyl triethoxy silane coupling modified calcium sulfate whisker; comparative example 2 replaces the modified lignin with lignin of equal mass compared to comparative example 1; compared with comparative example 1, the modified polypropylene in comparative example 3 is an epoxy resin grafted PP-g-MAH; the modified polypropylene in comparative example 4 was replaced with equal mass of PP-g-MAH as compared with comparative example 1. The foam materials obtained in comparative examples 1 to 4 have reduced tensile strength, compressive strength and limiting oxygen index data compared with example 1, and it is understood that the inventive arrangement of the foam material components and processes thereof can promote the comprehensive improvement of mechanical properties and flame retardant properties thereof.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The preparation process of the environment-friendly polypropylene flame-retardant foam material is characterized by comprising the following steps of: the method comprises the following steps:
extruding polypropylene, ultra-high molecular weight polyethylene, modified polypropylene and an antioxidant through a double-screw extruder, and granulating to obtain master batches;
adding calcium sulfate whisker, mixing at high speed for 5-10 min, extruding by a single screw, and injecting carbon dioxide to foam to obtain a foam material;
the modified polypropylene is prepared by the following process:
taking polypropylene grafted maleic anhydride, flame-retardant epoxy resin, zinc acetylacetonate and antioxidant 1010, extruding by a single screw at 187-192 ℃ to obtain modified polypropylene;
the flame-retardant epoxy resin is prepared by the following process:
mixing ethanol and amino lignin, slowly adding 2-thiazolyl propanal, heating to 65-80 ℃ after finishing adding within 30min, and reacting for 5-6 h; DOPO is added, heated to 80-85 ℃ and reacted for 12-13 h to obtain modified lignin;
and heating the epoxy resin to 130-150 ℃, adding the modified lignin, and stirring for reaction for 30-40 min to obtain the flame-retardant epoxy resin.
2. The process for preparing the environment-friendly polypropylene flame-retardant foam material according to claim 1, which is characterized in that: the foam material comprises the following components in parts by mass: 80 to 100 parts of polypropylene, 12 to 15 parts of ultra-high molecular weight polyethylene, 10 to 30 parts of modified polypropylene, 0.8 to 1.2 parts of calcium sulfate whisker and 0.2 to 0.5 part of antioxidant.
3. The process for preparing the environment-friendly polypropylene flame-retardant foam material according to claim 1, which is characterized in that: the calcium sulfate whisker is subjected to surface modification, and the specific process is as follows:
mixing gamma-glycidoxypropyl trimethoxy silane and methanol, regulating the pH of the system to 7.8-8.2, carrying out hydrolysis reaction at 40-42 ℃ for 100-150 min, adding calcium sulfate whisker, and heating to 138-142 ℃ for 100-150 min; adding amino lignin and phosphoric acid, and reacting for 2-4 hours at 30-50 ℃ to obtain the modified calcium sulfate whisker.
4. The process for preparing the environment-friendly polypropylene flame-retardant foam material according to claim 3, which is characterized in that: the mass ratio of the calcium sulfate whisker to the gamma-glycidyl ether oxypropyl trimethoxysilane to the amino lignin to the phosphoric acid is 100 (5-8): 60-85): 0.85-1.33.
5. The process for preparing the environment-friendly polypropylene flame-retardant foam material according to claim 3, which is characterized in that: the amino lignin is prepared by the following process:
mixing deionized water, ethanol and OP-10, stirring for 12-18 min, adding lignin, stirring and mixing for 12-18 min, regulating the pH of the system to 3-4 by using hydrochloric acid, slowly adding 3-aminopropyl dimethyl methoxysilane, and reacting for 12-24 h at 38-42 ℃.
6. The process for preparing the environment-friendly polypropylene flame-retardant foam material according to claim 1, which is characterized in that: the modified polypropylene comprises the following components in parts by mass: 100 parts of polypropylene grafted maleic anhydride, 6-22 parts of flame-retardant epoxy resin, 0.1-0.2 part of catalyst zinc acetylacetonate and 0.5-1.0 part of antioxidant 1010.
7. The process for preparing the environment-friendly polypropylene flame-retardant foam material according to claim 1, which is characterized in that: the mass ratio of the amino lignin to the 2-thiazolyl propanal to the DOPO is 100 (10-21) (15.5-32.0);
the mass ratio of the epoxy resin to the modified lignin is 100 (10-25).
8. An environmentally friendly polypropylene flame retardant foam material prepared according to any one of claims 1-7.
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