CN112080083A

CN112080083A - High-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material and preparation method thereof

Info

Publication number: CN112080083A
Application number: CN202010958241.2A
Authority: CN
Inventors: 韩志才; 高玉伟
Original assignee: Tianjin Jiatai Weiye Chemical Industry Co ltd
Current assignee: Tianjin Jiatai Weiye Chemical Industry Co ltd
Priority date: 2020-09-14
Filing date: 2020-09-14
Publication date: 2020-12-15

Abstract

The invention discloses a high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material which comprises the following raw materials in parts by weight: 70-100 parts of styrene, 150-240 parts of desalted water, 5-7.6 parts of foaming agent, 0.2-0.7 part of initiator, 0.1-0.5 part of nucleating agent, 0.5-4.5 parts of flame retardant, 0.01-0.08 part of inorganic sodium salt, 0.01-3 parts of graphite, 0.05-0.2 part of inorganic suspending agent, 0.0001-0.0005 part of organic suspending agent, 0.001-0.005 part of dispersing agent, 0.01-2 parts of inorganic additive, 0.001-0.005 part of pH regulator and 0.003-0.005 part of bead distribution regulator. The product obtained by the invention has less powdery particles, the combustion performance completely meets the requirement of B level in the grading of combustion performance of building materials and products, and the product has good flame-retardant and fireproof performance and heat-insulating performance; and has excellent mechanical properties while ensuring the flame-retardant and heat-insulating properties.

Description

High-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material and preparation method thereof

Technical Field

The invention relates to the field of composite materials, in particular to a high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material and a preparation method thereof.

Background

Building energy conservation is one of important ways for reducing environmental pollution and solving energy crisis, and a passive house is an important opportunity and platform for promoting building energy conservation work in China as a brand-new energy-saving building concept. The lower energy consumption standard of the passive house is realized by building outer walls with high heat insulation and sound insulation and strong sealing performance and renewable energy. The Expandable Polystyrene (EPS) foam insulation board has the advantages of heat insulation, unique buffer shock resistance, aging resistance, waterproofness, light weight, low price and the like, so that the Expandable Polystyrene (EPS) foam insulation board is applied to the field of building energy-saving materials.

However, EPS heat-insulating material often contains olefin substances, and polystyrene has relatively low thermal deformation temperature (70-98 ℃), is easy to burn quickly after ignition, and is decomposed to generate a large amount of toxic gas; meanwhile, the current EPS heat-insulating material also has the problems of weaker mechanical properties such as tensile strength and the like. At present, a large amount of flame retardant is often added into EPS heat insulation materials used in the domestic construction industry to improve the flame retardant performance, but the defects that the stability and the mechanical property of the materials are damaged due to the addition of too much flame retardant are overcome. Therefore, it is highly desirable to develop a high-efficiency flame-retardant and heat-insulating expandable polystyrene and graphite composite material with excellent mechanical properties.

Disclosure of Invention

In order to solve the technical problems, the invention provides a high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material, which comprises the following raw materials in parts by weight: 70-100 parts of styrene, 150-240 parts of desalted water, 5-7.6 parts of foaming agent, 0.2-0.7 part of initiator, 0.1-0.5 part of nucleating agent, 0.5-4.5 parts of flame retardant, 0.01-0.08 part of inorganic sodium salt, 0.01-3 parts of graphite, 0.05-0.2 part of inorganic suspending agent, 0.0001-0.0005 part of organic suspending agent, 0.001-0.005 part of dispersing agent, 0.01-2 parts of inorganic additive, 0.001-0.005 part of pH regulator and 0.003-0.005 part of bead distribution regulator.

As a preferable technical scheme, the initiator is selected from one or more of benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl-2-ethylhexyl carbonate peroxide, dicumyl peroxide, di-tert-butylcyclohexyl peroxydicarbonate and azobisisobutyronitrile.

As a preferable technical scheme, the particle size of the graphite is 1-50 μm.

As a preferable technical solution, the graphite is surface-treated graphite.

As a preferable technical scheme, the organic suspending agent is selected from one or more of hydroxyethyl cellulose, gelatin, starch, methyl cellulose and hydroxymethyl cellulose.

As a preferable technical scheme, the inorganic suspending agent is selected from one or more of activated calcium phosphate, magnesium carbonate, magnesium phosphate and barium sulfate.

As a preferable technical scheme, the weight ratio of the graphite to the organic suspending agent to the inorganic suspending agent is 1: (0.0001-0.02): (0.06-10).

As a preferable technical scheme, the dispersing agent is polyvinyl alcohol and/or polypropylene alcohol.

As a preferred technical scheme, the raw material further comprises an auxiliary agent; the auxiliary agent is selected from one or more of a lubricant, an antistatic agent, a reducing agent, a plasticizer, a film coating agent, a synergistic flame retardant and a plastic stabilizer.

The second aspect of the invention provides a preparation method of the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material, which comprises the following steps:

the method comprises the following steps: keeping the rotating speed of 50-70 r/min, adding an inorganic suspending agent, an organic suspending agent, an inorganic sodium salt, graphite and an inorganic additive, stirring for 20-40 min, continuing adding styrene, a nucleating agent, a flame retardant, a pH regulator and an initiator, stirring for 20-40 min, adding desalted water and a dispersing agent into a reaction kettle, stirring for 20-40 min at 90 ℃, and cooling to normal temperature to obtain an aqueous suspension;

step two: heating the aqueous suspension obtained in the step one to 85-90 ℃, preserving heat for 0.5-1.5 h, adding a bead distribution regulator, and preserving heat for 5-6 h to obtain a mixed suspension material;

step three: adding a stabilizer into the mixed suspended material obtained in the second step until the mixed suspended material is stable, filling nitrogen into the reaction kettle, adding a foaming agent, continuously heating to 115-130 ℃, keeping the temperature for 2-2.5 hours under the pressure of 0.8-0.9 MPa, and cooling to 30-40 ℃ to obtain a bead material;

step four: and (4) dehydrating, drying and packaging the bead material obtained in the step three to obtain the high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material.

Has the advantages that: the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material with excellent performance is prepared by using styrene, graphite, an inorganic suspending agent, an organic suspending agent and other auxiliaries. The product obtained by the invention has less powdery particles, and after the product is prepared into a polystyrene (EPS) plate, the combustion performance completely meets the requirement of B level in the classification of combustion performance of building materials and products, and the product has good flame-retardant and fireproof performance and heat-insulating performance; and has excellent mechanical properties while ensuring the flame-retardant and heat-insulating properties.

Detailed Description

The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.

The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

In a preferred embodiment, the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material comprises the following raw materials in parts by weight: 95 parts of styrene, 160 parts of desalted water, 6.3 parts of foaming agent, 0.3 part of initiator, 0.2 part of nucleating agent, 2.0 parts of flame retardant, 0.03 part of inorganic sodium salt, 0.01 part of graphite, 0.1 part of inorganic suspending agent, 0.0002 part of organic suspending agent, 0.002 part of dispersing agent, 0.05 part of inorganic additive, 0.002 part of pH regulator and 0.004 part of bead distribution regulator.

< styrene >

Styrene (Styrene), CAS number 100-42-5, is an organic compound formed by substituting one hydrogen atom of ethylene with benzene, and is an industrially important monomer for synthetic resins, ion exchange resins, synthetic rubbers, and the like.

The styrene is not particularly limited in the present invention, and various styrenes known to those skilled in the art may be used, and may be purchased from, for example, zileu petrochemical.

< desalted Water >

Desalted water (desalted water) is water that has had the strong electrolyte contained therein removed or reduced to some extent.

In a preferred embodiment, the conductivity of the desalinated water is below 3 μ s/cm.

In a more preferred embodiment, the conductivity of the desalinated water is 1 μ s/cm.

The μ s/cm, microsiemens per centimeter, is a unit of conductivity and is a parameter used to describe the ease of charge flow in a substance. The method for measuring the conductivity is not particularly limited in the present invention, and various conductivity measuring methods known to those skilled in the art, for example, a conductivity meter, may be used. The method for controlling the conductivity of the desalted water is also not particularly limited, and various methods for controlling the conductivity, such as reverse osmosis/ion exchange resin treatment, well known to those skilled in the art, can be used.

< blowing agent >

In a preferred embodiment, the blowing agent is isopentane and/or n-pentane.

In a more preferred embodiment, the blowing agent is a mixture of isopentane and n-pentane.

In a preferred embodiment, the weight ratio of isopentane to n-pentane is 1: (2-3).

In a more preferred embodiment, the weight ratio of isopentane to n-pentane is 1: 2.3.

in a preferred embodiment, the feedstock further comprises an adjuvant.

< initiator >

In a preferred embodiment, the initiator is selected from the group consisting of benzoyl peroxide (CAS number 94-36-0), t-butyl peroxybenzoate (CAS number 614-45-9), t-amyl peroxy-2-ethylhexyl carbonate (CAS number 70833-40-8), dicumyl peroxide (CAS number 80-43-3), di-t-butylcyclohexyl peroxydicarbonate (CAS number 15520-11-3), azobisisobutyronitrile (CAS number 78-67-1), and combinations of one or more thereof.

In a more preferred embodiment, the initiator is selected from the group consisting of benzoyl peroxide, t-butyl peroxybenzoate, t-amyl-2-ethylhexyl carbonate peroxide, dicumyl peroxide, and combinations thereof.

In a further preferred embodiment, the initiator is a mixture of benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl-2-ethylhexyl carbonate peroxide, dicumyl peroxide.

In a preferred embodiment, the weight ratio of the benzoyl peroxide to the tert-butyl peroxybenzoate to the tert-amyl-2-ethylhexyl peroxycarbonate to the dicumyl peroxide is (5-7): (1-2): (1-2): (2.5-4).

In a more preferred embodiment, the weight ratio of benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl-2-ethylhexyl carbonate peroxide and dicumyl peroxide is 6: 1.5: 1.5: 3.25.

< nucleating agent >

Nucleating agents, namely polyethylene waxes, CAS number 9002-88-4, are an additive for polyolefin processing.

In a preferred embodiment, the molecular weight of the nucleating agent is 500 to 5000.

In a more preferred embodiment, the molecular weight of the nucleating agent is 2000 to 2500.

In a further preferred embodiment, the molecular weight of the nucleating agent is 2250.

The molecular weight, i.e., relative molecular mass, is not particularly limited in the present invention, and various molecular weight measurement methods known to those skilled in the art, such as gel permeation chromatography, can be used. The polyethylene wax can be purchased from Qingdao Haoho chemical Co., Ltd, for example, the polyethylene wax is H100P, and the molecular weight is 2000-2500 (the average molecular weight is 2250).

< flame retardant >

In a preferred embodiment, the flame retardant is selected from the group consisting of tris (2-chloropropyl) phosphate (flame retardant TCPP), tris (1, 3-dichloropropyl) phosphate (flame retardant TDCPP), hexabromocyclododecane (flame retardant HBCD), melamine cyanurate salt (flame retardant MCA), tris (2, 3-dibromopropyl) isocyanurate (flame retardant TBC), melamine polyphosphate (flame retardant MPP), decabromodiphenylethane, ammonium polyphosphate, decabromodiphenyl ether, zinc borate in combination with one or more thereof.

< inorganic sodium salt >

In a preferred embodiment, the inorganic sodium salt is selected from the group consisting of trisodium phosphate, tetrasodium phosphate, sodium sulfate, sodium dichromate, in combination with one or more.

In a more preferred embodiment, the inorganic sodium salt is tetrasodium phosphate.

The said tetrasodium phosphate, also known as sodium pyrophosphate, has CAS number 7722-88-5.

< graphite >

In a preferred embodiment, the graphite has a particle size of 1 to 50 μm.

In a more preferred embodiment, the graphite has a particle size of 20 to 30 μm.

In a further preferred embodiment, the particle size of the graphite is 25 μm.

The graphite is commercially available, for example from Qingdao Shuofeng graphite products, Inc., and has a particle size of 25 μm.

In a preferred embodiment, the graphite is surface-treated graphite.

In a preferred embodiment, the method for preparing the surface-treated graphite comprises the following steps: adding 0.65-0.93 part by weight of graphite and 0.65-0.9 part by weight of surfactant into 50-60 parts by weight of pure water, heating to 65-75 ℃, stirring for 10-14 h, washing with water, and drying to obtain the catalyst.

In a more preferred embodiment, the method for preparing the surface-treated graphite comprises the following steps: adding 0.79 part by weight of graphite and 0.77 part by weight of surfactant into 55 parts by weight of pure water, heating to 70 ℃, stirring for 12 hours, washing with water, and drying to obtain the graphite.

In a preferred embodiment, the surfactant is a sulfonate surfactant.

In a more preferred embodiment, the sulfonate surfactant is selected from the group consisting of sodium dodecylbenzenesulfonate (CAS number 25155-30-0), sodium lignosulfonate (CAS number 8061-51-6), sodium dibutylnaphthalenesulfonate (CAS number 25417-20-3), sodium diisopropylnaphthalenesulfonate (CAS number 1322-93-6), and combinations of one or more thereof.

In a further preferred embodiment, the sulfonate surfactant is sodium lignosulfonate (CAS number 8061-51-6).

The sodium lignosulfonate is commercially available, for example, from shengfujiang technologies ltd, tianjin, under the model MN.

The inventor finds that the graphite treated by the sulfonate surfactant can improve the dispersion stability of the graphite to a certain extent and improve the flame retardant property and the heat conductivity coefficient of the material at the same time in a long-term research and development process. The specific annular hydrophobic structure of the sulfonate surfactant sodium lignosulfonate can coat the graphite layer by layer, and meanwhile, the long molecular chain is partially inserted into the coating structure, so that the range of the hydrophobic group is increased, and the stability of a styrene oil-in-water system is improved; atoms in the same plane in the unique lamellar structure of the graphite are combined by covalent bonds, and the graphite can play a good role in reflecting infrared rays under the condition of good dispersion, so that the heat conductivity coefficient of the EPS foam material is further reduced; and the graphite dispersed in the system can also absorb alpha hydrogen atoms activated on the main chain skeleton when the polystyrene is heated, and cooperates with the flame retardant to promote the surface of the material to form a continuous and compact carbon layer, so that the contact between the material and the outside air can be isolated while the outside heat is blocked, and the addition of the graphite improves the carbon forming property of the material, thereby improving the flame retardant property of the material and reducing the generation of combustible volatile products. However, the van der waals force between adjacent layers in the graphite is weak, and the long chain of the sodium lignosulfonate molecule influences the intermolecular force of the polymer to a certain extent, so that the mechanical property of the obtained material cannot meet the application standard of the expandable polystyrene.

< inorganic suspending agent >

In a preferred embodiment, the inorganic suspending agent is selected from one or more of activated calcium phosphate, magnesium carbonate, magnesium phosphate, barium sulfate in combination.

In a more preferred embodiment, the inorganic suspending agent is activated calcium phosphate.

In a preferred embodiment, the activated calcium phosphate is surface treated activated calcium phosphate.

In a preferred embodiment, the preparation method of the surface-treated activated calcium phosphate comprises the following steps: mixing active calcium phosphate, a dispersing agent and water according to the weight ratio of 1: (0.05-0.12): (50-60) putting the mixture into a container, stirring the mixture at 50-70 ℃ until the active calcium phosphate is uniformly mixed, and drying the mixture to obtain the surface-treated active calcium phosphate.

In a more preferred embodiment, the method for preparing the surface-treated activated calcium phosphate comprises the following steps: mixing active calcium phosphate, polyol type surfactant and water according to the weight ratio of 1: 0.08: 55 parts by weight of the active calcium phosphate is put into a container, stirred at 60 ℃ until the active calcium phosphate is uniformly mixed, and dried to obtain the surface-treated active calcium phosphate.

The active calcium phosphate, i.e. the suspending agent TCP, has a molecular formula of Ca₂(PO4)₆(OH)₂It is a water-insoluble inorganic fine powder.

In a preferred embodiment, the polyol-type surfactant is selected from a combination of one or more of pentaerythritol fatty acid ester, lauric acid monoglyceride (CAS No. 142-18-7), glycerin fatty acid ester (CAS No. 542-44-9), and polyglycerin-6 stearate (CAS No. 95461-65-7).

In a more preferred embodiment, the polyol-type surfactant is lauric monoglyceride.

The inventor unexpectedly finds that when the inorganic suspending agent is the active calcium phosphate treated by the polyalcohol type surfactant, the suspension rate of the system is not reduced, the mechanical property and the flame retardant property of the obtained material are obviously improved, and the thermal conductivity of the obtained material can be reduced. The inventor conjectures the possible reason that on one hand, the long-chain alkyl chain on the molecular surface of the active calcium phosphate treated by the polyol type surfactant lauric acid monoglyceride can be inserted into the graphite coating structure and is in staggered fit with the long chain of the sodium lignosulfonate molecule, so that the stability of the system is improved, the sodium lignosulfonate molecule is promoted to be adsorbed on the particle surface, the gap of the network structure of the system is filled, and the mechanical property of the obtained material is obviously improved; on the other hand, the treated active calcium phosphate can also cooperate with graphite to form a heat insulation aggregation structure, so that the heat conductivity of the obtained material is reduced, and the active group on the larger specific surface area of the material also provides a certain amount of activated alpha hydrogen atom binding points, so that the formation of a continuous and compact carbon layer on the surface of the material is further promoted, and the flame retardant property of the obtained material is improved. However, at the same time, the specific active calcium phosphate and graphite after surface treatment cause too much mechanical isolation of styrene during forming liquid drops, and too much powder particles are easily generated, which is a big problem that the inventor has to solve.

< organic suspending agent >

In a preferred embodiment, the organic suspending agent is selected from one or more of hydroxyethylcellulose, gelatin, starch, methylcellulose, hydroxymethylcellulose in combination.

In a more preferred embodiment, the organic suspending agent is hydroxyethyl cellulose (CAS number 9004-62-0).

In a preferred embodiment, the weight ratio of the graphite to the organic suspending agent to the inorganic suspending agent is 1: (0.0001-0.02): (0.06-10).

In a more preferred embodiment, the weight ratio of the graphite to the organic suspending agent to the inorganic suspending agent is 1: 0.02: 10.

< dispersant >

In a preferred embodiment, the dispersant is polyvinyl alcohol and/or polypropylene alcohol.

In a more preferred embodiment, the dispersant is polyvinyl alcohol.

In a preferred embodiment, the alcoholysis degree of the polyvinyl alcohol is 87 to 89 mole%.

In a more preferred embodiment, the degree of alcoholysis of the polyvinyl alcohol is 88 mole%.

The polyvinyl alcohol (PVA) has a CAS number of 9002-89-5 of PVA-217 of Colorado Japan, and the alcoholysis degree of 87-89 mole% (the average value is 88 mole%). The alcoholysis degree refers to the mole percentage of hydroxyl groups in the original groups in the product obtained after alcoholysis, and the method for testing the alcoholysis degree is not particularly limited in the present invention, and various methods for testing the alcoholysis degree, such as NaOH titration, which are well known to those skilled in the art, can be used.

The inventor unexpectedly finds out in the further exploration practice that when the weight ratio of graphite, organic suspending agent and inorganic suspending agent is 1: (0.0001-0.02): (0.06-10), and when the alcoholysis degree of the dispersant polyvinyl alcohol is 87-89 mole%, the mechanical property of the obtained material is further improved, and the content of the bead material is also greatly improved. The possible reason is that when dispersant polyvinyl alcohol with alcoholysis degree of 87-89 mole% is used, the hydroxyethyl cellulose of the organic suspending agent can be partially dissolved in the water phase and wraps the surface of the treated graphite and the activated calcium phosphate of the inorganic suspending agent, so that the small liquid drops are promoted to be bonded into normal-size liquid drops again; and for the monomer liquid drop with larger size, the monomer liquid drop can only be adsorbed on the surface of the liquid drop due to the limitation of the coating capability of the monomer liquid drop, and a liquid film protective layer is formed between a small part of the sodium lignosulfonate molecular chain and the monolaurin monoglyceride molecular chain on the surface of the liquid drop, so that the content of the bead material in the obtained material is greatly improved.

< inorganic additive >

The inorganic additives are not particularly limited, and various inorganic additives such as one or a combination of more of carbon black, white carbon black and mica powder can be selected according to the situation.

< pH adjuster >

The pH adjuster is not particularly limited in the present invention, and various pH adjusters may be used as appropriate, and may include at least one of sodium bicarbonate, ammonium carbonate, sodium hydroxide, ammonium hydroxide, dimethylaminoethanol, and calcium carbonate.

< bead distribution modifier >

The bead distribution regulator is a reagent for regulating and controlling suspended particles to be between 0.5 and 5mm in the field of expandable polystyrene.

The bead distribution modifier is not particularly limited in the present invention, and various bead distribution modifiers known to those skilled in the art, such as sodium bisulfite, can be used.

< auxiliary agent >

In a more preferred embodiment, the raw material further comprises 0.41-0.65 parts by weight of an auxiliary agent.

In a further preferred embodiment, the raw material further comprises 0.53 parts by weight of an auxiliary.

In a preferred embodiment, the adjuvant is selected from the group consisting of one or more of lubricants, antistatic agents, reducing agents, plasticizers, film coating agents, synergistic flame retardants, plastic stabilizers.

In a more preferred embodiment, the adjuvants are lubricants and antistatic agents.

In a further preferred embodiment, the weight ratio of the lubricant to the antistatic agent is (6 to 25): 1.

in a still further preferred embodiment, the lubricant and antistatic agent are present in a weight ratio of 14: 1.

the antistatic agent is not particularly limited in the present invention, and various antistatic agents well known in the art, such as polyethylene glycol PEG-400, can be used.

In a preferred embodiment, the lubricant is zinc stearate and monoglycerides (CAS number 123-94-4).

In a more preferred embodiment, the weight ratio of zinc stearate to monoglyceride is (1-2.5): 1.

in a further preferred embodiment, the weight ratio of zinc stearate to monoglyceride is 1.5: 1.

In a preferred embodiment, the preparation method of the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material comprises the following steps:

the method comprises the following steps: keeping the rotating speed of 60r/min, adding an inorganic suspending agent, an organic suspending agent, inorganic sodium salt, graphite and an inorganic additive, stirring for 30min, continuing adding styrene, a nucleating agent, a flame retardant, a pH regulator and an initiator, stirring for 30min, adding desalted water and a dispersing agent into a reaction kettle, stirring for 30min at 90 ℃, and cooling to normal temperature to obtain an aqueous suspension;

step two: heating the aqueous suspension obtained in the step one to 90 ℃, preserving the heat for 1h, adding a bead distribution regulator, and preserving the heat for 5.3h to obtain a mixed suspension material;

step three: adding a stabilizer into the mixed suspended material obtained in the second step until the mixed suspended material is stable, filling nitrogen into the reaction kettle, adding a foaming agent, continuously heating to 122.5 ℃, keeping the temperature for 2.2 hours under the pressure of 0.85MPa, and cooling to 35 ℃ to obtain a bead material;

In another preferred embodiment, the preparation method of the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material comprises the following steps:

step four: and (4) dewatering and drying the bead material obtained in the step three, putting the bead material into a mixer, adding an auxiliary agent, stirring for 10min, and packaging to obtain the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material.

The stabilizer is not particularly limited in the present invention, and various stabilizers well known to those skilled in the art, such as the suspending agent TCP, may be used. The stable state of the mixed suspended material means that the particle sinking phenomenon does not occur in the suspended material any longer.

The high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material is a high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite bead material, and is prepared into a corresponding material according to actual requirements in the subsequent use, such as a polystyrene (EPS) foam heat-insulation board.

The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.

Examples

Example 1

The embodiment 1 of the invention provides a high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material, which comprises the following raw materials in parts by weight: 95 parts of styrene, 160 parts of desalted water, 6.3 parts of foaming agent, 0.3 part of initiator, 0.2 part of nucleating agent, 2.0 parts of flame retardant, 0.03 part of inorganic sodium salt, 0.01 part of graphite, 0.1 part of inorganic suspending agent, 0.0002 part of organic suspending agent, 0.002 part of dispersing agent, 0.05 part of inorganic additive, 0.002 part of pH regulator and 0.004 part of bead distribution regulator.

The conductivity of the desalted water was 1. mu.s/cm. The foaming agent is a mixture of isopentane and n-pentane, and the weight ratio of the isopentane to the n-pentane is 1: 2.3. the initiator is a mixture of benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl peroxide-2-ethylhexyl carbonate and dicumyl peroxide, and the weight ratio of the four is 6: 1.5: 1.5: 3.25. the nucleating agent is polyethylene wax which is purchased from Qingdao Hao chemical Co., Ltd, has the model of H100P, and has the molecular weight of 2000-2500 (the average molecular weight is 2250). The flame retardant is decabromodiphenylethane. The inorganic sodium salt is tetrasodium phosphate. The dispersant is polyvinyl alcohol with alcoholysis degree of 88mole percent and is PVA-217 of Coly, Japan. The inorganic additive is white carbon black which is German Wake white carbon black N20. The pH regulator is sodium bicarbonate. The organic suspending agent is hydroxyethyl cellulose; the bead distribution regulator is sodium bisulfite.

The particle size of the graphite is 25 μm, and the graphite is surface-treated graphite. The preparation method of the graphite after surface treatment comprises the following steps: adding 0.79 part by weight of graphite and 0.77 part by weight of sodium lignosulfonate into 55 parts by weight of pure water, heating to 70 ℃, stirring for 12 hours, washing with water, and drying to obtain the graphite.

The inorganic suspending agent is active calcium phosphate after surface treatment, and the preparation method comprises the following steps: mixing activated calcium phosphate, lauric acid monoglyceride and water according to the weight ratio of 1: 0.08: 55 parts by weight of the active calcium phosphate is put into a container, stirred at 60 ℃ until the active calcium phosphate is uniformly mixed, and dried to obtain the surface-treated active calcium phosphate.

The embodiment also provides a preparation method of the high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material, which comprises the following steps:

Example 2

Embodiment 2 of the invention provides a high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material, which comprises the following raw materials in parts by weight: 70 parts of styrene, 150 parts of desalted water, 5 parts of foaming agent, 0.2 part of initiator, 0.1 part of nucleating agent, 0.5 part of flame retardant, 0.01 part of inorganic sodium salt, 0.01 part of graphite, 0.05 part of inorganic suspending agent, 0.0001 part of organic suspending agent, 0.001 part of dispersing agent, 0.01 part of inorganic additive, 0.001 part of pH regulator and 0.003 part of bead distribution regulator.

The conductivity of the desalted water was 1. mu.s/cm. The foaming agent is a mixture of isopentane and n-pentane, and the weight ratio of the isopentane to the n-pentane is 1: 2. the initiator is a mixture of benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl peroxide-2-ethylhexyl carbonate and dicumyl peroxide, and the weight ratio of the four is 5: 1: 1: 2.5. the nucleating agent is polyethylene wax which is purchased from Qingdao Hao chemical Co., Ltd, has the model of H100P, and has the molecular weight of 2000-2500 (the average molecular weight is 2250). The flame retardant is decabromodiphenylethane. The inorganic sodium salt is tetrasodium phosphate. The dispersant is polyvinyl alcohol with alcoholysis degree of 88mole percent and is PVA-217 of Coly, Japan. The inorganic additive is white carbon black which is German Wake white carbon black N20. The pH regulator is sodium bicarbonate. The organic suspending agent is hydroxyethyl cellulose; the bead distribution regulator is sodium bisulfite.

The particle size of the graphite is 20 μm, and the graphite is surface-treated. The preparation method of the graphite after surface treatment comprises the following steps: adding 0.65 weight part of graphite and 0.65 weight part of sodium lignosulfonate into 50 weight parts of pure water, heating to 65 ℃, stirring for 10 hours, washing with water, and drying to obtain the graphite.

The inorganic suspending agent is active calcium phosphate after surface treatment, and the preparation method comprises the following steps: mixing activated calcium phosphate, lauric acid monoglyceride and water according to the weight ratio of 1: 0.05: 50 parts by weight of the active calcium phosphate is put into a container, stirred at 50 ℃ until the active calcium phosphate is uniformly mixed, and dried to obtain the surface-treated active calcium phosphate.

the method comprises the following steps: keeping the rotating speed of 50r/min, adding an inorganic suspending agent, an organic suspending agent, inorganic sodium salt and graphite, stirring for 20min, continuing to add styrene, polyethylene wax and an initiator, stirring for 20min, adding desalted water and a dispersing agent into a reaction kettle, stirring for 20min at 90 ℃, and cooling to normal temperature to obtain an aqueous suspension;

step two: heating the aqueous suspension obtained in the step one to 85 ℃, preserving the temperature for 0.5h, adding a bead distribution regulator, and preserving the temperature for 5h to obtain a mixed suspension material;

step three: adding a suspending agent TCP into the mixed suspended material obtained in the second step until the mixed suspended material is stable, filling nitrogen into the reaction kettle, adding a foaming agent, continuously heating to 115 ℃, keeping the temperature for 2 hours under the pressure of 0.8MPa, and cooling to 30 ℃ to obtain a bead material;

Example 3

Embodiment 3 of the present invention provides a high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material, which comprises the following raw materials in parts by weight: 100 parts of styrene, 240 parts of desalted water, 7.6 parts of foaming agent, 0.7 part of initiator, 0.5 part of nucleating agent, 4.5 parts of flame retardant, 0.08 part of inorganic sodium salt, 3 parts of graphite, 0.2 part of inorganic suspending agent, 0.0005 part of organic suspending agent, 0.005 part of dispersing agent, 2 parts of inorganic additive, 0.005 part of pH regulator and 0.005 part of bead distribution regulator.

The conductivity of the desalted water was 1. mu.s/cm. The foaming agent is a mixture of isopentane and n-pentane, and the weight ratio of the isopentane to the n-pentane is 1: 3. the initiator is a mixture of benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl peroxide-2-ethylhexyl carbonate and dicumyl peroxide, and the weight ratio of the four is 7: 2: 2: 4. the nucleating agent is polyethylene wax which is purchased from Qingdao Hao chemical Co., Ltd, has the model of H100P, and has the molecular weight of 2000-2500 (the average molecular weight is 2250). The flame retardant is decabromodiphenylethane. The inorganic sodium salt is tetrasodium phosphate. The dispersant is polyvinyl alcohol with alcoholysis degree of 88mole percent and is PVA-217 of Coly, Japan. The inorganic additive is white carbon black which is German Wake white carbon black N20. The pH regulator is sodium bicarbonate. The organic suspending agent is hydroxyethyl cellulose; the bead distribution regulator is sodium bisulfite.

The particle size of the graphite is 30 μm, which is the graphite after surface treatment. The preparation method of the graphite after surface treatment comprises the following steps: adding 0.93 part by weight of graphite and 0.9 part by weight of sodium lignosulfonate into 60 parts by weight of pure water, heating to 75 ℃, stirring for 14 hours, washing with water, and drying to obtain the graphite.

The inorganic suspending agent is active calcium phosphate after surface treatment, and the preparation method comprises the following steps: mixing activated calcium phosphate, lauric acid monoglyceride and water according to the weight ratio of 1: 0.12: 60 parts by weight of the active calcium phosphate is put into a container, stirred at 70 ℃ until the active calcium phosphate is uniformly mixed, and dried to obtain the surface-treated active calcium phosphate.

the method comprises the following steps: keeping the rotating speed at 70r/min, adding an inorganic suspending agent, an organic suspending agent, inorganic sodium salt and graphite, stirring for 40min, continuing to add styrene, polyethylene wax and an initiator, stirring for 40min, adding desalted water and a dispersing agent into a reaction kettle, stirring for 40min at 90 ℃, and cooling to normal temperature to obtain an aqueous suspension;

step two: heating the aqueous suspension obtained in the step one to 90 ℃, preserving the heat for 1.5h, adding a bead distribution regulator, and preserving the heat for 6h to obtain a mixed suspension material;

step three: adding a suspending agent TCP into the mixed suspended material obtained in the second step until the mixed suspended material is stable, filling nitrogen into the reaction kettle, adding a foaming agent, continuously heating to 130 ℃, keeping the temperature for 2.5 hours under the pressure of 0.8-0.9 MPa, and cooling to 40 ℃ to obtain a bead material;

Example 4

Example 4 of the present invention provides a high efficiency flame retardant and heat insulating expandable polystyrene and graphite composite material, the specific implementation thereof is similar to example 1, except that the particle size of the graphite is replaced by 1 μm from 25 μm.

Example 5

Example 5 of the present invention provides a high efficiency flame retardant and heat insulating expandable polystyrene and graphite composite material, the specific implementation thereof is similar to example 1, except that the particle size of the graphite is changed from 25 μm to 50 μm.

Example 6

Embodiment 6 of the present invention provides a high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material, and the specific implementation manner thereof is similar to embodiment 1, except that sodium lignosulfonate in the preparation method of the graphite subjected to surface treatment is replaced by sodium dodecylbenzenesulfonate (CAS number 25155-30-0).

Example 7

Example 7 of the present invention provides a high efficiency flame retardant heat insulating expandable polystyrene and graphite composite material, the specific implementation thereof is similar to example 1, except that the particle size of the graphite is changed from 25 μm to 0.5 μm.

Example 8

Example 8 of the present invention provides a high efficiency flame retardant heat insulating expandable polystyrene and graphite composite material, the specific implementation thereof is similar to example 1, except that the particle size of the graphite is changed from 25 μm to 55 μm.

Example 9

Embodiment 9 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, and a specific embodiment thereof is similar to embodiment 1, except that sodium lignosulfonate in the preparation method of the graphite after surface treatment is replaced with sodium dodecylsulfonate (CAS number 2386-53-0).

Example 10

Embodiment 10 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, and a specific embodiment of the efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material is similar to embodiment 1, except that 0.77 parts by weight of sodium lignosulfonate in the preparation method of the graphite after surface treatment is replaced with 0 parts by weight of sodium lignosulfonate.

Example 11

Example 11 of the present invention provides a high efficiency flame retardant heat insulating expandable polystyrene and graphite composite material, the specific implementation thereof is similar to example 1, except that the weight part of the graphite is replaced by 0 part from 2.75 parts.

Example 12

Embodiment 12 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, and a specific embodiment thereof is similar to embodiment 1, except that lauric acid monoglyceride in the preparation method of surface-treated activated calcium phosphate is replaced with sodium dodecyl sulfate (CAS No. 2386-53-0).

Example 13

Embodiment 13 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, and the specific implementation manner thereof is similar to that in embodiment 1, except that lauric acid monoglyceride is not added in the preparation method of the surface-treated activated calcium phosphate.

Example 14

Example 14 of the present invention provides a high efficiency flame retardant heat insulating expandable polystyrene and graphite composite material, the specific implementation manner of which is similar to example 1, except that the weight part of the inorganic suspending agent active calcium phosphate is changed from 0.25 part to 0 part.

Example 15

Embodiment 15 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, which is implemented in a similar manner to embodiment 1, except that the inorganic suspending agent is 0.01 part by weight of active calcium phosphate.

Example 16

Example 16 of the present invention provides a high efficiency flame retardant and heat insulating expandable polystyrene and graphite composite material, the specific implementation manner of which is similar to example 1, except that the weight part of the inorganic suspending agent active calcium phosphate is changed from 0.25 part to 0.25 part.

Example 17

Embodiment 17 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, and the specific implementation manner is similar to that in embodiment 1, except that the weight part of the organic suspending agent hydroxyethyl cellulose is replaced by 0.1 part.

Example 18

Example 18 of the present invention provides a high efficiency flame retardant heat insulating expandable polystyrene and graphite composite material, the specific implementation manner of which is similar to example 1, except that the weight part of the organic suspending agent hydroxyethyl cellulose is replaced by 0.001 part from 0.1 part.

Example 19

Embodiment 19 of the present invention provides a high efficiency flame retardant heat insulation expandable polystyrene and graphite composite material, which is similar to embodiment 1, except that the dispersant is a polyvinyl alcohol with alcoholysis degree of 88 mole% replaced with a polyvinyl alcohol with alcoholysis degree of 98.5 mole%, which is a PVA-105 of gorgeous japan, and the alcoholysis degree is 98-99 mole% (average value is 98.5 mole%).

Example 20

Embodiment 20 of the present invention provides a high efficiency flame retardant heat insulation expandable polystyrene and graphite composite material, which comprises the following raw materials in parts by weight: 95 parts of styrene, 160 parts of desalted water, 6.3 parts of foaming agent, 0.3 part of initiator, 0.2 part of nucleating agent, 2.0 parts of flame retardant, 0.03 part of inorganic sodium salt, 0.01 part of graphite, 0.1 part of inorganic suspending agent, 0.0002 part of organic suspending agent, 0.002 part of dispersing agent, 0.05 part of inorganic additive, 0.002 part of pH regulator, 0.004 part of bead distribution regulator, 0.29 part of zinc stearate, 0.225 part of monoglyceride and 0.015 part of polyethylene glycol (PEG-400).

Example 21

Embodiment 21 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, and a specific embodiment thereof is similar to embodiment 1, except that the weight parts of zinc stearate are replaced by 0.25 part from 0.29 part, the weight parts of monoglyceride are replaced by 0.15 part from 0.225 part, and the weight parts of polyethylene glycol (PEG-400) are replaced by 0.015 part to 0.01 part.

Example 22

Embodiment 22 of the present invention provides an efficient flame-retardant heat-insulating expandable polystyrene and graphite composite material, and a specific implementation manner thereof is similar to that in embodiment 1, except that the weight parts of zinc stearate are replaced by 0.33 part from 0.29 part, the weight parts of monoglyceride are replaced by 0.30 part from 0.225 part, and the weight parts of polyethylene glycol (PEG-400) are replaced by 0.015 part to 0.02 part.

Evaluation of Performance

1. Content testing of bead material: after the high-efficiency flame-retardant heat-insulating expandable polystyrene obtained in examples 1 to 22 and the graphite composite material are uniformly mixed, 10 positions are randomly selected from the mixture to obtain samples until the samples just cover the bottom of the whole culture dish (with the size of 60mm), and the content of the bead materials in the samples is evaluated. If the content of the bead material is more than or equal to 90 percent, the bead material is evaluated as good; if the bead content is < 90%, it is marked as X.

2. Flame retardant property:

testing critical thermal radiation flux: after a polystyrene plate sample with the size of 1050mm long, 230mm wide and 60mm thick is prepared from the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material obtained in the embodiments 1-22 by a method well known to those skilled in the art according to GB/T11785 and 2005 "method for combustion performance radiant heat source of flooring material", a radiant flux (CHF) at a flame-off position or a radiant flux (HF-30) corresponding to a farthest position where flame propagates during a test of 30MIN is obtained through a test, and the lowest value of the two is selected as a critical radiant flux.

20s internal flame tip height Fs test: after the high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material obtained in the examples 1 to 22 is prepared into a polystyrene board sample with the length of 250mm, the width of 90mm and the thickness of 60mm according to GB/T8626 'flammability test method for building materials' by adopting a method well known by a person skilled in the art, the flame tip height Fs is tested for 20s by adopting a surface ignition mode in a combustion box at the air flow rate of 0.7 m/s.

Thirdly, grading the combustion performance: according to the detection data, the burning performance of the sample is graded according to GB8624-2012 'grading of burning performance of building materials and products'. Wherein the B level is that the critical heat radiation flux is more than or equal to 8.0kW/m²The height Fs of the flame tip within 20s is less than or equal to 150 mm; the C level is that the critical heat radiation flux is more than or equal to 4.5kW/m²The height Fs of the flame tip within 20s is less than or equal to 150 mm; d level is that the critical heat radiation flux is more than or equal to 3.0kW/m²The height Fs of the flame tip within 20s is less than or equal to 150 mm; the critical heat radiation flux of the E grade is more than or equal to 2.2kW/m²The height Fs of the flame tip within 20s is less than or equal to 150 mm; if the above requirements are not met, the result is marked as F, and the result is shown in Table 1.

3. And (3) testing the heat conductivity coefficient: the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite materials obtained in examples 1 to 16 and 20 to 21 are prepared into polystyrene plate samples with the dimensions of 250mm long, 90mm wide and 60mm thick according to GB/T10294-2008 'Heat insulating material steady-state thermal resistance and related characteristic determination protective hot plate method' by adopting a method well known by a person skilled in the art, and then a heat conductivity coefficient determinator is adopted to determine the heat conductivity coefficient. After three tests, the average value was calculated, and the results are shown in table 1.

4. And (3) testing mechanical properties: the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material obtained in examples 1 to 22 is made into a dumbbell shape according to GB9641-1988, rigid foam tensile property test method, and tensile property test is performed at 25 ℃ by using a tester by a method well known to those skilled in the art, and the results are shown in Table 1.

Table 1 results of performance testing

The combination of the above experimental results shows that: the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material with excellent performance is prepared by using styrene, graphite, an inorganic suspending agent, an organic suspending agent and other auxiliaries. The content test of the bead material shows that the content of the bead material is more than or equal to 90 percent, and the powdery particles are less; the flame retardant property test shows that the combustion performance of the flame retardant fully reaches B level, and the flame retardant has good flame retardant and fireproof performance; the heat conductivity coefficient test shows that the heat conductivity coefficient is 0.026-0.032W/(m.K), and the heat insulation performance is excellent; mechanical property tests show that the tensile strength is 0.15-0.35 MPa, and the flame retardant and heat insulation performance is ensured, and meanwhile, the mechanical property is excellent.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. The invention is not limited to the embodiments described above, but rather, many modifications and variations may be made by one skilled in the art without departing from the scope of the invention.

Claims

1. The high-efficiency flame-retardant heat-insulation expandable polystyrene and graphite composite material is characterized by comprising the following raw materials in parts by weight: 70-100 parts of styrene, 150-240 parts of desalted water, 5-7.6 parts of foaming agent, 0.2-0.7 part of initiator, 0.1-0.5 part of nucleating agent, 0.5-4.5 parts of flame retardant, 0.01-0.08 part of inorganic sodium salt, 0.01-3 parts of graphite, 0.05-0.2 part of inorganic suspending agent, 0.0001-0.0005 part of organic suspending agent, 0.001-0.005 part of dispersing agent, 0.01-2 parts of inorganic additive, 0.001-0.005 part of pH regulator and 0.003-0.005 part of bead distribution regulator.

2. The high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material as claimed in claim 1, wherein the initiator is selected from one or more of benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl-2-ethylhexyl carbonate peroxide, dicumyl peroxide, di-tert-butylcyclohexyl peroxydicarbonate and azobisisobutyronitrile.

3. The high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material as claimed in claim 1, wherein the particle size of the graphite is 1-50 μm.

4. The high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material as claimed in claim 1, wherein the graphite is surface-treated graphite.

5. The high efficiency, flame retardant, thermal insulating, expandable polystyrene and graphite composite of claim 1, wherein the organic suspending agent is selected from the group consisting of hydroxyethylcellulose, gelatin, starch, methylcellulose, hydroxymethylcellulose, and combinations thereof.

6. The high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material as claimed in claim 1, wherein the inorganic suspending agent is selected from one or more of activated calcium phosphate, magnesium carbonate, magnesium phosphate and barium sulfate.

7. The high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material as claimed in any one of claims 1 to 6, wherein the weight ratio of the graphite to the organic suspending agent to the inorganic suspending agent is 1: (0.0001-0.02): (0.06-10).

8. The high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material as claimed in claim 1, wherein the dispersant is polyvinyl alcohol and/or polypropylene alcohol.

9. The high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material as claimed in claim 1, wherein the raw materials further comprise an auxiliary agent; the auxiliary agent is selected from one or more of a lubricant, an antistatic agent, a reducing agent, a plasticizer, a film coating agent, a synergistic flame retardant and a plastic stabilizer.

10. The preparation method of the high-efficiency flame-retardant heat-insulating expandable polystyrene and graphite composite material according to any one of claims 1 to 8, characterized by comprising the following steps: