CN107474166B - A kind of polystyrene silver gray thermal insulation material preparation method of mica titanium filling in situ - Google Patents

A kind of polystyrene silver gray thermal insulation material preparation method of mica titanium filling in situ Download PDF

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CN107474166B
CN107474166B CN201710732012.7A CN201710732012A CN107474166B CN 107474166 B CN107474166 B CN 107474166B CN 201710732012 A CN201710732012 A CN 201710732012A CN 107474166 B CN107474166 B CN 107474166B
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mica titanium
polystyrene
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thermal insulation
insulation material
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CN107474166A (en
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闫俊涛
王春蕾
李建芬
范国枝
宋光森
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Wuhan Polytechnic University
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    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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Abstract

The invention belongs to energy-saving and heat-insulating material fields, and in particular to a kind of polystyrene silver gray thermal insulation material of mica titanium filling in situ.1) preparation method of the material is the following steps are included: use the in-situ low-temperature hydrophobic modification techniques of water phase mica titanium, using water as decentralized medium, it is modified that surface hydrophobicity is carried out to raw material mica titanium powder using hydrophobic modifier, then filtered, be dried in vacuo to obtain lipophilic mica titanium powder；2) suspension polymerisation filling in situ technique is utilized, it disperses oil system auxiliary material in water system auxiliary material under mechanical agitation, heating carries out polymerization reaction, foaming agent is added in the polymerization later period, heating continues polymerization to particle hardening, washing and obtains expandability mica titanium polystyrene compound particle, foamed molding again obtains the polystyrene silver gray thermal insulation material of mica titanium filling in situ.Present invention process is simple, compound particle size tunable, low in cost, organic solvent-free, environmentally friendly, easy industrialized production.

Description

A kind of polystyrene silver gray thermal insulation material preparation method of mica titanium filling in situ
Technical field
The invention belongs to energy-saving and heat-insulating material fields, and in particular to a kind of polystyrene silver gray of mica titanium filling in situ Thermal insulation material preparation method.
Background technique
As thermal insulation material market competition is increasingly sharpened, building exterior wall heat preserving field keeps the temperature expanded polystyrene (EPS) (EPS) More stringent requirements are proposed for the thermal insulation property and flame retardant property of material.To comply with China's energy-saving and emission-reduction strategy, while meeting heat preservation The needs that building materials fire-protection rating is promoted.Urgent need develops a kind of high performance EPS product, can reduce refrigeration and warming cost, Reduce the discharge of carbon dioxide, and the flame retardant property of energy Synchronous lifting EPS.The polyphenyl of mica titanium filling in situ prepared by the present invention Ethylene silver gray thermal insulation material has excellent heat preservation and insulation and flame retardant property, and the technical matters is simple, is easy to industrialize Production.Currently, the technical report of the domestic polystyrene silver gray thermal insulation material without mica titanium filling in situ.
Currently, generalling use following two method preparation mica titanium Polystyrene heat insulation material.First method is surface Coating coats a stratus master slice in the outer layer of EPS insulation board, and this method must be kept the temperature mica sheet and EPS using adhesive Plate is bonded together, and volatile toxic solvent is contained in adhesive, pollutes environment, is also easy to destroy EPS insulating plate structure, technique is multiple Miscellaneous, application field is significantly limited.Second method is that comminution granulation is blended, using blending technology by polystyrene and mica titanium powder Heating melting, the preparation of the processes such as blended, extruding pelletization, foaming agent dipping, foaming, still, mica titanium powder and polyphenyl The interface compatibility of ethylene is very poor, it is difficult to and it is evenly dispersed in polystyrene matrix, greatly reduce the mechanical property of polystyrene Can, furthermore complex procedures of the technique, at high cost, it is difficult to be widely applied.Therefore the present invention, which bases oneself upon, solves asking in above-mentioned technique Topic, devises preparation method, its product and the application of a kind of polystyrene silver gray thermal insulation material of mica titanium filling in situ.
Summary of the invention
To solve the deficiencies in the prior art, the present invention provides a kind of polystyrene silver gray of mica titanium filling in situ guarantors The preparation method of adiabator, its product and application.
A kind of preparation method of the polystyrene silver gray thermal insulation material of mica titanium filling in situ, comprising the following steps:
1) the in-situ low-temperature hydrophobically modified of water phase mica titanium
Using water as decentralized medium, under mechanical agitation, mica titanium powder is dispersed in water, in certain modified temperature Degree is lower to be added hydrophobic modifier, carries out hydrophobically modified to mica titanium surface, then filtered, be dried in vacuo to obtain lipophilic mica titanium Powder；
2) preparation of the polystyrene silver gray thermal insulation material of mica titanium filling in situ
Under mechanical agitation, disperses oil system auxiliary material in water system auxiliary material, be to slowly warm up to polymerization temperature and gathered Reaction is closed, foaming agent is added in the polymerization later period, heating continues polymerization to particle hardening, washing and obtains expandability mica titanium polystyrene Compound particle, then foamed molding obtain the polystyrene silver gray thermal insulation material of mica titanium filling in situ, in which:
Oil system auxiliary material includes the lipophilic mica titanium valve that styrene monomer, initiator, fire retardant and step 1) obtain Body；
The water system auxiliary material includes deionized water, without owner's suspending agent, inorganic suspension aid, water soluble polymer suspending agent And surfactant.
Specifically, in step 1):
The mica titanium is the composite granule that sheet black mica surface is crossed through nanometer titanium dioxide-coated；
The hydrophobic modifier is octadecenic acid, hexadecanol, octadecyl alcolol, polyethylene glycol phosphate or polypropylene glycol phosphoric acid Any one in ester, preferably octadecenic acid.
Specifically, in step 2):
The initiator is selected from one of benzoyl peroxide or azodiisobutyronitrile, preferably benzoyl peroxide first Acyl.
Any one of the fire retardant in hexabromocyclododecane or deca-BDE or both mixing, preferably Hexabromocyclododecane；
Any one of no owner's suspending agent in active calcium phosphate, talcum powder or kaolin, it is preferably living Property calcium phosphate；
Any one of the inorganic suspension aid in anhydrous sodium sulfate or anhydrous slufuric acid hydrogen sodium, it is preferably anhydrous Sodium sulphate；
The water soluble polymer suspending agent is selected from polyvinyl alcohol, hydroxyethyl cellulose, polyacrylate, polyethylene pyrrole Any one in pyrrolidone, gelatin or cellulose ether, preferably polyvinyl alcohol；
The surfactant is selected from anionic surfactant sodium dodecylbenzene sulfonate, anionic surfactant ten Dialkyl sulfonates, nonionic surfactant nonylphenol polyoxyethylene ether or nonionic surfactant octylphenol polyethylene ethylene oxide Any one in ether, preferably neopelex.
Preferably, in step 1), modification temperature is 55~65 DEG C；In step 2), it is to slowly warm up to polymerization temperature 85~89 DEG C, heating rate is 0.5~1 DEG C/min.
Further, in step 2), after system reaches polymerization temperature, no owner's suspending agent is added for the first time；Work as polymerization When process enters suspension polymerisation critical days, no owner's suspending agent and surfactant are added for the second time.
Specifically, addition for the first time is any in active calcium phosphate, talcum powder or kaolin without owner's suspending agent One kind, preferably active calcium phosphate；
Second addition without any one in active calcium phosphate, talcum powder or kaolin of owner's suspending agent, it is excellent Choosing is active calcium phosphate；
The surfactant of second of addition is selected from anionic surfactant sodium dodecylbenzene sulfonate, anionic surface Activating agent dodecyl sodium sulfate, nonionic surfactant nonylphenol polyoxyethylene ether or nonionic surfactant octyl phenol Any one in polyoxyethylene ether, preferably neopelex.
Preferably, the polystyrene silver gray thermal insulation material of mica titanium filling in situ preparation method the following steps are included:
1) the in-situ low-temperature hydrophobically modified of water phase mica titanium
400~800g of deionized water, mica titanium 40~160g of powder are sequentially added in a kettle, and cloverleaf agitating paddle turns 100~300 revs/min of speed, is sufficiently stirred dispersion 10~25 minutes, is heated to 55~65 DEG C of modification temperature, and hydrophobic modifier is added 1.0~4.0g reacts 25~35 minutes, and cooling simultaneously stops stirring, and suction filtration, vacuum drying obtain lipophilic mica titanium powder, puts It purchases use；
2) preparation of the polystyrene silver gray thermal insulation material of mica titanium filling in situ
2a) water system auxiliary material: successively into autoclave be added 300~500g of deionized water, without owner's suspending agent 0.5~ 4.0g, inorganic 0.5~2.0g of suspension aid, mass fraction are 0.02~0.05% 5~15g of aqueous surfactant solution, quality Score be 6.0~10.0% water soluble polymer suspending agents 15~30g of aqueous solution, mechanical stirring revolving speed be 150~300 turns/ Point, pre-dispersed 5~10 minutes；
2b) oil system auxiliary material: in advance by 150~250g of styrene monomer, 1.5~2.5g of initiator, fire retardant 3.0~9.0 It is uniformly mixed, 2.0~10.0g of lipophilic mica titanium powder that step 1) obtains then is added, after being uniformly dispersed, be by all oil Auxiliary material be added step 2a) where reaction kettle in, the air being passed through in nitrogen purge reaction kettle, adjust rotating speed of agitator be 150 ~300 revs/min, make styrene monomer droplet under Compositional type suspending agent, surfactant and mechanical stirring shear action, with The size suspended dispersed of design in water, is to slowly warm up to 85~89 DEG C of polymerization temperature, and heating rate is 0.5~1 DEG C/ Min adds 0.5~4.0g of no owner's suspending agent, and after reaction 1.5~2.5 hours, suspension polymerisation critical days need to be added inorganic again Main 0.5~4.0g of suspending agent and mass fraction are 0.02~0.05% 1.0~5.0g of aqueous surfactant solution, and protection polymerize Monomer droplet do not increase, be indeformable, reacting balance carry out, and by constantly sampling observation polymer particles growing way and size. As polymerized monomer conversion ratio increases, mica titanium powder is equably anchored in polystyrene matrix；
2c) foaming agent is filled: 10~20g of foaming agent pentane being added into step 2a) reaction kettle, closes charging and sampling Mouthful, temperature is gradually risen to 108~114 DEG C, and the reaction was continued 4~6h, pentane is fully penetrated into polystyrene matrix, and monomer is poly- It closes completely, it is fully hardened by sampling observation expandability mica titanium polystyrene compound particle, stop reaction；
2d) wash: cooling discharging, by the expandability mica titanium polystyrene compound particle of synthesis with 6~10% hydrochloric acid Aqueous solution and clear water washing, remove the Inorganic suspending agent on surface；
2e) foaming: foaming is carried out to expandability mica titanium polystyrene compound particle with vapor and obtains cloud Female titanium polystyrene silver gray thermal insulation material.
Further, in step 1), dehydrated alcohol is additionally added as hydrophobically modified when 1.0~4.0g of hydrophobic modifier is added The cosolvent of agent, corresponding additive amount are 0.5~2.0g.
The present invention also provides the polystyrene for the mica titanium filling in situ being prepared according to above-mentioned preparation method is silver grey Color thermal insulation material.
The present invention also provides the applications of the polystyrene silver gray thermal insulation material of above-mentioned mica titanium filling in situ, for making Make building exterior wall heat preserving plate or foam insulation box.
Preparation method provided by the present invention is stirred first with the in-situ low-temperature hydrophobic modification techniques of water phase mica titanium in machinery Mix under effect, by mica titanium dispersion in deionized water, be added hydrophobic modifier, under lower modification temperature react to get To hydrophobicity mica titanium powder.Suspension polymerisation filling in situ technique is used again, directly by modified lipophilic mica titanium powder It is scattered in styrene monomer, adds initiator and fire retardant composition oil system auxiliary material, it then, will under mechanical agitation Oil system auxiliary material is scattered in by deionized water, surfactant, without owner's suspending agent, inorganic suspension aid, water soluble polymer and hangs Floating agent, heated polymerization, later period are passed through foaming agent, and polymerization obtains expandability mica titanium polystyrene compound particle completely, foam Molding obtains mica titanium polystyrene silver gray thermal insulation material.The reflective thermal radiation of sheet mica titanium and heat-insulated oxygen barrier properties, can Further decrease Polystyrene heat insulation material thermal coefficient be 0.031~0.034W/mK, improve heat insulation effect, while Flame retardant property is improved to a certain extent, it is fire-retardant up to B1 grades.Present invention process is simple, compound particle size tunable, low in cost, nothing Organic solvent, environmentally friendly, easy industrialized production.
Detailed description of the invention
Fig. 1 is the optical photograph for the lipophilic mica titanium powder that provided preparation method obtains according to the present invention.
Fig. 2 is lipophilic mica titanium powder electron scanning under low power that provided preparation method obtains according to the present invention Electromicroscopic photograph.
Fig. 3 is lipophilic mica titanium powder electron scanning under high power that provided preparation method obtains according to the present invention Electromicroscopic photograph.
Fig. 4 is the light for the expandability mica titanium polystyrene compound particle that provided preparation method obtains according to the present invention Learn photo.
Fig. 5 is the expandability mica titanium polystyrene compound particle foaming that provided preparation method obtains according to the present invention Optical photograph afterwards.
Fig. 6 is the light for the mica titanium polystyrene silver gray thermal insulation material that provided preparation method obtains according to the present invention Learn photo.
Fig. 7 is the electricity in the mica titanium Polystyrene heat insulation material cross section that provided preparation method obtains according to the present invention Sub- stereoscan photograph.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and illustrated embodiment is served only for explaining the present invention, It is not intended to limit the scope of the present invention.
Embodiment 1
1) the in-situ low-temperature hydrophobically modified of water phase mica titanium
Sequentially add deionized water 500g, mica titanium powder 50g in a kettle, 200 turns of cloverleaf rotating speed of agitator/ Point, dispersion 12 minutes is sufficiently stirred, is heated to 57 DEG C of modification temperature, hydrophobic modifier octadecenic acid 1.2g, dehydrated alcohol is added 0.6g reacts 30 minutes, and cooling simultaneously stops stirring, and suction filtration, vacuum drying obtain lipophilic mica titanium powder, places spare.
2) preparation of the polystyrene silver gray thermal insulation material of mica titanium filling in situ
2a) water system auxiliary material: deionized water 470g is successively added into autoclave, without owner's suspending agent active calcium phosphate 1.0g, inorganic suspension aid natrium carbonicum calcinatum 1.0g, mass fraction are 0.02% sodium dodecyl benzene sulfonate aqueous solution 6.0g, matter The aqueous solution 18g that score is 8.0% polyvinyl alcohol is measured, mechanical stirring revolving speed is 180 revs/min, pre-dispersed 5 minutes；
Styrene monomer 200g, initiator 2.0g, fire retardant 4.0g: being uniformly mixed by 2b) oil system auxiliary material in advance, then plus Enter the lipophilic mica titanium powder 4.0g that step 1) obtains, after being uniformly dispersed, step 2a be added in all oil systems auxiliary material) where In reaction kettle, the air being passed through in nitrogen purge reaction kettle, adjusting rotating speed of agitator is 200 revs/min, makes the small liquid of styrene monomer Drop is dispersed in suspension within water under Compositional type suspending agent, surfactant and mechanical stirring shear action with the size of design In, 86 DEG C of polymerization temperature are to slowly warm up to, no owner's suspending agent active calcium phosphate 1.0g is added, after reaction 1.5 hours, is suspended poly- Critical days is closed, no owner's suspending agent active calcium phosphate 1.2g need to be added again and mass fraction is 0.02% neopelex Aqueous solution 3.0g protects the monomer droplet polymerizeing do not increase, is indeformable, reacting balance progress, and passes through constantly sampling observation The growing way and size of polymer particles.As polymerized monomer conversion ratio increases, mica titanium powder is equably anchored on polystyrene In matrix；
2c) foaming agent is filled: foaming agent pentane 12g is added into step 2a) reaction kettle, closes charging and sample tap, by High-temperature edge up to 108 DEG C, the reaction was continued 6.0h, pentane is fully penetrated into polystyrene matrix, and monomer polymerization is complete, passes through Sampling observation expandability mica titanium polystyrene compound particle is fully hardened, stops reaction；
2d) wash: cooling discharging, the expandability mica titanium polystyrene compound particle of synthesis is water-soluble with 6% hydrochloric acid Liquid and clear water washing, remove the Inorganic suspending agent on surface；
2e) foaming: foaming is carried out to expandability mica titanium polystyrene compound particle with vapor and obtains cloud Female titanium polystyrene silver gray thermal insulation material.
Obtained mica titanium polystyrene silver gray thermal insulation material is measured, thermal coefficient can reach 0.034W/m K。
Embodiment 2
1) the in-situ low-temperature hydrophobically modified of water phase mica titanium
Sequentially add deionized water 500g, mica titanium powder 60g in a kettle, 200 turns of cloverleaf rotating speed of agitator/ Point, dispersion 13 minutes is sufficiently stirred, is heated to 58 DEG C of modification temperature, hydrophobic modifier octadecenic acid 1.5g, dehydrated alcohol is added 0.8g reacts 28 minutes, and cooling simultaneously stops stirring, and suction filtration, vacuum drying obtain lipophilic mica titanium powder, places spare.
2) preparation of the polystyrene silver gray thermal insulation material of mica titanium filling in situ
2a) water system auxiliary material: deionized water 500g is successively added into autoclave, without owner's suspending agent kaolin 1.2g, inorganic suspension aid anhydrous sodium sulfate 1.2g, mass fraction are 0.02% sodium dodecyl benzene sulfonate aqueous solution 8.0g, matter The aqueous solution 20g that score is 8.0% polyvinyl alcohol is measured, mechanical stirring revolving speed is 230 revs/min, pre-dispersed 6 minutes；
Styrene monomer 200g, initiator 2.1g, fire retardant 4.0g: being uniformly mixed by 2b) oil system auxiliary material in advance, then plus Enter the lipophilic mica titanium powder 6.0g that step 1) obtains, after being uniformly dispersed, step 2a be added in all oil systems auxiliary material) where In reaction kettle, the air being passed through in nitrogen purge reaction kettle, adjusting rotating speed of agitator is 200 revs/min, makes the small liquid of styrene monomer Drop is dispersed in suspension within water under Compositional type suspending agent, surfactant and mechanical stirring shear action with the size of design In, 87 DEG C of polymerization temperature are to slowly warm up to, no owner's suspending agent kaolin 1.2g is added, after reaction 1.8 hours, suspension polymerisation danger The dangerous phase need to add no owner's suspending agent kaolin 1.2g again and mass fraction is 0.02% sodium dodecyl benzene sulfonate aqueous solution 2.0g protects the monomer droplet polymerizeing do not increase, is indeformable, reacting balance progress, and passes through constantly sampling observation polymerization grain The growing way and size of son.As polymerized monomer conversion ratio increases, mica titanium powder is equably anchored in polystyrene matrix；
2c) foaming agent is filled: foaming agent pentane 11g is added into step 2a) reaction kettle, closes charging and sample tap, by High-temperature edge up to 109 DEG C, the reaction was continued 5.5h, pentane is fully penetrated into polystyrene matrix, and monomer polymerization is complete, passes through Sampling observation expandability mica titanium polystyrene compound particle is fully hardened, stops reaction；
2d) wash: cooling discharging, the expandability mica titanium polystyrene compound particle of synthesis is water-soluble with 7% hydrochloric acid Liquid and clear water washing, remove the Inorganic suspending agent on surface；
2e) foaming: foaming is carried out to expandability mica titanium polystyrene compound particle with vapor and obtains cloud Female titanium polystyrene silver gray thermal insulation material.
Obtained mica titanium polystyrene silver gray thermal insulation material is measured, thermal coefficient can reach 0.033W/m K。
Embodiment 3
1) the in-situ low-temperature hydrophobically modified of water phase mica titanium
Sequentially add deionized water 400g, mica titanium powder 70g in a kettle, 240 turns of cloverleaf rotating speed of agitator/ Point, dispersion 20 minutes is sufficiently stirred, is heated to 63 DEG C of modification temperature, hydrophobic modifier octadecyl alcolol 2.8g, dehydrated alcohol is added 0.9g reacts 28 minutes, and cooling simultaneously stops stirring, and suction filtration, vacuum drying obtain lipophilic mica titanium powder, places spare.
2) preparation of the polystyrene silver gray thermal insulation material of mica titanium filling in situ
2a) water system auxiliary material: deionized water 450g is successively added into autoclave, without owner's suspending agent 1.4g, inorganic Suspension aid 1.4g, mass fraction are 0.02% nonylphenol polyoxyethylene ether aqueous solution 10.0g, mass fraction is 8.0% hydroxyl second The aqueous solution 23g of base cellulose, mechanical stirring revolving speed are 240 revs/min, pre-dispersed 8 minutes；
Styrene monomer 200g, initiator 2.2g, fire retardant 6.0g: being uniformly mixed by 2b) oil system auxiliary material in advance, then plus Enter the lipophilic mica titanium powder 7.0g that step 1) obtains, after being uniformly dispersed, step 2a be added in all oil systems auxiliary material) where In reaction kettle, the air being passed through in nitrogen purge reaction kettle, adjusting rotating speed of agitator is 250 revs/min, makes the small liquid of styrene monomer Drop is dispersed in suspension within water under Compositional type suspending agent, surfactant and mechanical stirring shear action with the size of design In, 88 DEG C of polymerization temperature are to slowly warm up to, no owner's suspending agent active calcium phosphate 1.5g is added, after reaction 2.2 hours, is suspended poly- Critical days is closed, no owner's suspending agent active calcium phosphate 1.5g need to be added again and mass fraction is 0.02% nonylphenol polyoxyethylene ether Aqueous solution 3.0g protects the monomer droplet polymerizeing do not increase, is indeformable, reacting balance progress, and passes through constantly sampling observation The growing way and size of polymer particles.As polymerized monomer conversion ratio increases, mica titanium powder is equably anchored on polystyrene In matrix；
2c) foaming agent is filled: foaming agent pentane 11g is added into step 2a) reaction kettle, closes charging and sample tap, by High-temperature edge up to 112 DEG C, the reaction was continued 5.0h, pentane is fully penetrated into polystyrene matrix, and monomer polymerization is complete, passes through Sampling observation expandability mica titanium polystyrene compound particle is fully hardened, stops reaction；
2d) wash: cooling discharging, the expandability mica titanium polystyrene compound particle of synthesis is water-soluble with 9% hydrochloric acid Liquid and clear water washing, remove the Inorganic suspending agent on surface；
2e) foaming: foaming is carried out to expandability mica titanium polystyrene compound particle with vapor and obtains cloud Female titanium polystyrene silver gray thermal insulation material.
Obtained mica titanium polystyrene silver gray thermal insulation material is measured, thermal coefficient can reach 0.031W/m K。
Effect example
As Fig. 1 be according to the present invention provided by lipophilicity mica titanium powder obtained in preparation method optical photograph, From photo it can be seen that lipophilic mica titanium is black powder.
As Fig. 2 be according to the present invention provided by the obtained lipophilic mica titanium powder of preparation method electronics under low power sweep Retouch electromicroscopic photograph, it is known that mica titanium is laminated structure, and particle size is in 10-40um.
As Fig. 3 be according to the present invention provided by the obtained electronics under high power of lipophilic mica titanium powder of preparation method Stereoscan photograph, it is known that there are many nanoscale small particles on mica titanium surface, and the small particles on surface are TiO 2 particles, piece Shape mica titanium has the characteristic of reflective thermal radiation and heat-insulating flame-retardant.
As Fig. 4 be according to the present invention provided by preparation method obtain expandability mica titanium polystyrene compound particle Optical photograph, particle are appearance of black, and particle size is uniform, average grain diameter about 0.7mm.
As Fig. 5 be according to the present invention provided by preparation method obtain expandability mica titanium polystyrene compound particle hair Optical photograph after bubble, particle are the ball-type appearance of rule, average grain diameter about 4.0mm.
As Fig. 6 be according to the present invention provided by preparation method obtain mica titanium polystyrene silver gray thermal insulation material Optical photograph, the insulation board of preparation are silver gray, and sheet mica titanium has reflective thermal radiation characteristic, can substantially reduce insulation board Thermal coefficient, improves heat insulation effect, the insulative properties of sheet mica titanium can effectively trap heat and oxygen transmitting, Synchronous lifting its Flame retardant effect is significantly better than common white insulation board.
As Fig. 7 be according to the present invention provided by preparation method obtain mica titanium Polystyrene heat insulation material cross section Electron scanning electromicroscopic photograph, it is known that the abscess of expanded particle is uniform, and cavity is clear-cut, has preferable insulation abscess unit.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (8)

1. a kind of preparation method of the polystyrene silver gray thermal insulation material of mica titanium filling in situ, which is characterized in that including with Lower step:
1) the in-situ low-temperature hydrophobically modified of water phase mica titanium
Using water as decentralized medium, under mechanical agitation, mica titanium powder is dispersed in water, under certain modification temperature Hydrophobic modifier is added, hydrophobically modified is carried out to mica titanium surface, then filtered, be dried in vacuo to obtain lipophilic mica titanium valve Body；
The mica titanium powder is the composite granule that sheet black mica surface is crossed through nanometer titanium dioxide-coated；Described dredges Water modifying agent is any one in octadecenic acid, hexadecanol, octadecyl alcolol, polyethylene glycol phosphate or polypropylene glycol phosphate；
2) preparation of the polystyrene silver gray thermal insulation material of mica titanium filling in situ
It disperses oil system auxiliary material in water system auxiliary material under mechanical agitation, is to slowly warm up to polymerization temperature and polymerize instead It answers, polymerization later period addition foaming agent, heating continue to polymerize compound to particle hardens, washing obtains expandability mica titanium polystyrene Particle, then foamed molding obtain the polystyrene silver gray thermal insulation material of mica titanium filling in situ, in which:
Oil system auxiliary material includes the lipophilic mica titanium powder that styrene monomer, initiator, fire retardant and step 1) obtain；
The water system auxiliary material includes deionized water, without owner's suspending agent, inorganic suspension aid, water soluble polymer suspending agent and table Face activating agent；
The initiator is selected from one of benzoyl peroxide or azodiisobutyronitrile；The fire retardant is selected from hexabromo ring 12 In alkane or deca-BDE any one or both it is compound；No owner's suspending agent be selected from active calcium phosphate, talcum powder or Any one in kaolin；Any one of the inorganic suspension aid in anhydrous sodium sulfate or anhydrous slufuric acid hydrogen sodium； The water soluble polymer suspending agent be selected from polyvinyl alcohol, hydroxyethyl cellulose, polyacrylate, polyvinylpyrrolidone, Any one in gelatin or cellulose ether；The surfactant is selected from anionic surfactant dodecyl benzene sulfonic acid Sodium, anionic surfactant dodecyl sodium sulfate, nonionic surfactant nonylphenol polyoxyethylene ether or nonionic table Any one in the activating agent octyl phenol polyoxyethylene ether of face.
2. a kind of preparation side of the polystyrene silver gray thermal insulation material of mica titanium filling in situ according to claim 1 Method, it is characterised in that: in step 1), modification temperature is 55~65 DEG C；In step 2), it is to slowly warm up to polymerization temperature 85~89 DEG C, heating rate is 0.5~1 DEG C/min.
3. a kind of preparation side of the polystyrene silver gray thermal insulation material of mica titanium filling in situ according to claim 2 Method, it is characterised in that: in step 2), after system reaches polymerization temperature, add no owner's suspending agent for the first time；Work as polymerization process When into suspension polymerisation critical days, no owner's suspending agent and surfactant are added for the second time.
4. a kind of preparation side of the polystyrene silver gray thermal insulation material of mica titanium filling in situ according to claim 3 Method, it is characterised in that: that adds for the first time is any one in active calcium phosphate, talcum powder or kaolin without owner's suspending agent Kind；Add for the second time without any one in active calcium phosphate, talcum powder or kaolin of owner's suspending agent；Second of benefit The surfactant added is selected from anionic surfactant sodium dodecylbenzene sulfonate, anionic surfactant dodecyl sulphur Appointing in sour sodium, nonionic surfactant nonylphenol polyoxyethylene ether or nonionic surfactant octyl phenol polyoxyethylene ether It anticipates one kind.
5. a kind of preparation side of the polystyrene silver gray thermal insulation material of mica titanium filling in situ according to claim 4 Method, which comprises the following steps:
1) the in-situ low-temperature hydrophobically modified of water phase mica titanium
400~800g of deionized water, mica titanium 40~160g of powder, cloverleaf rotating speed of agitator are sequentially added in a kettle 100~300 revs/min, dispersion is sufficiently stirred 10~25 minutes, is heated to 55~65 DEG C of modification temperature, hydrophobic modifier 1.0 is added ~4.0g reacts 25~35 minutes, and cooling simultaneously stops stirring, and suction filtration, vacuum drying obtain lipophilic mica titanium powder, places standby With；
2) preparation of the polystyrene silver gray thermal insulation material of mica titanium filling in situ
2a) water system auxiliary material: successively into autoclave be added 300~500g of deionized water, without owner's suspending agent 0.5~ 4.0g, inorganic 0.5~2.0g of suspension aid, mass fraction are 0.02~0.05% 5~15g of aqueous surfactant solution, quality Score be 6.0~10.0% water soluble polymer suspending agents 15~30g of aqueous solution, mechanical stirring revolving speed be 150~300 turns/ Point, pre-dispersed 5~10 minutes；
2b) oil system auxiliary material: 150~250g of styrene monomer, 1.5~2.5g of initiator, fire retardant 3.0~9.0 are mixed in advance Uniformly, 2.0~10.0g of lipophilic mica titanium powder that step 1) obtains then is added, after being uniformly dispersed, by all oil systems auxiliary material Be added step 2a) where reaction kettle in, the air being passed through in nitrogen purge reaction kettle, adjust rotating speed of agitator be 150~300 Rev/min, make styrene monomer droplet under Compositional type suspending agent, surfactant and mechanical stirring shear action, with design Size suspended dispersed in water, be to slowly warm up to 85~89 DEG C of polymerization temperature, heating rate is 0.5~1 DEG C/min, is mended Add 0.5~4.0g of no owner's suspending agent, after reaction 1.5~2.5 hours, suspension polymerisation critical days need to add no owner again and suspend 0.5~4.0g of agent and mass fraction are 0.02~0.05% 1.0~5.0g of aqueous surfactant solution, protect the monomer polymerizeing Drop does not increase, is indeformable, reacting balance carries out, and by the growing way and size of constantly sampling observation polymer particles, with poly- It closes monomer conversion to increase, mica titanium powder is equably anchored in polystyrene matrix；
2c) foaming agent is filled: 10~20g of foaming agent pentane is added into step 2a) reaction kettle, closes charging and sample tap, by High-temperature edge up to 108~114 DEG C, the reaction was continued 4~6h, pentane is fully penetrated into polystyrene matrix, and monomer polymerization is complete Entirely, fully hardened by sampling observation expandability mica titanium polystyrene compound particle, stop reaction；
2d) wash: cooling discharging, the expandability mica titanium polystyrene compound particle of synthesis is water-soluble with 6~10% hydrochloric acid Liquid and clear water washing, remove the Inorganic suspending agent on surface；
2e) foaming: foaming is carried out to expandability mica titanium polystyrene compound particle with vapor and obtains mica titanium The polystyrene silver gray thermal insulation material of filling in situ.
6. the preparation method of the polystyrene silver gray thermal insulation material of mica titanium filling in situ according to claim 5, It is characterized in that: in step 1), being additionally added 0.5~2.0g of dehydrated alcohol when 1.0~4.0g of hydrophobic modifier is added and change as hydrophobic The cosolvent of property agent.
7. a kind of polyphenyl second for the mica titanium filling in situ that preparation method according to any one of claims 1 to 6 is prepared Alkene silver gray thermal insulation material.
8. a kind of a kind of polystyrene silver gray thermal insulation material of mica titanium filling in situ according to claim 7 is answered With, it is characterised in that: it is applied to production building exterior wall heat preserving plate or foam insulation box.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1084787A (en) * 1996-09-18 1998-04-07 Mitsubishi Chem Mkv Co Film for outdoor spreading
CN104817655A (en) * 2015-05-01 2015-08-05 李亮军 Production method for heat-insulating flame-resistant material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289519A (en) * 2008-06-10 2008-10-22 上海碧虎节能保温材料有限公司 Preparation of organic-inorganic composite foam material
US8535558B2 (en) * 2009-07-10 2013-09-17 Basf Se Microcapsules with polyvinyl monomers as crosslinker
CN101633709B (en) * 2009-08-27 2011-03-23 吉林大学 Method for preparing colorful polystyrene particle synthesized by in-situ suspension polymerization one-step process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1084787A (en) * 1996-09-18 1998-04-07 Mitsubishi Chem Mkv Co Film for outdoor spreading
CN104817655A (en) * 2015-05-01 2015-08-05 李亮军 Production method for heat-insulating flame-resistant material

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