CN105418877A - Ternary phyllosilicate-polyurethane nano-composite thermal insulation material and preparing method thereof - Google Patents
Ternary phyllosilicate-polyurethane nano-composite thermal insulation material and preparing method thereof Download PDFInfo
- Publication number
- CN105418877A CN105418877A CN201510953532.1A CN201510953532A CN105418877A CN 105418877 A CN105418877 A CN 105418877A CN 201510953532 A CN201510953532 A CN 201510953532A CN 105418877 A CN105418877 A CN 105418877A
- Authority
- CN
- China
- Prior art keywords
- kaolin
- nano
- compound
- polyurethane
- polynite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of a high polymer thermal insulation material, in particular to a ternary phyllosilicate-polyurethane nano-composite thermal insulation material and a preparing method thereof. The ternary phyllosilicate-polyurethane nano-composite thermal insulation material comprises following components in percent by weight: 90-95% of polyurethane, 2-7% of kaolin and 2-7% of imvite. The ternary phyllosilicate-polyurethane nano-composite thermal insulation material is obviously enhanced in thermal stability compared with pure organic polyurethane and is also superior to separately doped binary inorganic-polyurethane composite material. The ternary phyllosilicate-polyurethane nano-composite thermal insulation material is suitable for being used for thermal insulation of a thermal insulation layer of equipment or a device which is directly exposed to perpendicular incidence of the sun or is higher in operation temperature (such as a planar solar water heater, a heat collector and a water tank or an outdoor large-sized water tank); the preparing method of the composite thermal insulation material successfully solves the problem of easiness in separating out of a crystal due to poor dispersibility in a preparing reaction process of an inorganic nanomaterial.
Description
Technical field
The invention belongs to polymer thermal insulative field of material technology, be specifically related to ternary layered silicate-polyurethane nano compound insulating material and preparation method thereof.
Background technology
Hard polyurethane foams remains silent abscess for main urethane foam, there is low-down thermal conductivity, low relative density, certain hardness and intensity, also there is excellent sound insulation anti seismic efficiency, electrical properties is excellent, easy cutting, also possess certain water tolerance and erosion resistance, be widely used in building, furniture, automobile, shipbuilding, the industries such as petrochemical complex, especially due to its production and processing technology flexibly, excellent heat preservation property and lower production cost make it become the refrigerator of current main flow, refrigerator, surface duct, water heater conduit's water tank, the heat-insulating heat-preserving material of water vapour pipeline.Simultaneously, also poor heat resistance is there is in polyurethane foam as the pure organic insulation material of one, with use temperature and the time easily aging, poor dimensional stability, the feature of flame retardant properties difference, make that hard polyaminoester is yielding in exposed environments particularly hot environment, stability and security reduce, and then be restricted in actual use.Matrix material is by a kind of stable multiphase solid material of two or more physics combinations of substances different from chemical property, and the nano composite material military order hard polyaminoester be composited by inorganic silicate nano material and organic polymer obtains some performances that the aspect intrinsic polymer such as toughness reinforcing, fire-retardant, sterilization, high stability are undesirable or do not have.
Layer silicate mineral comprises chlorite, sepiolite, wilkinite, illite, polynite etc., its basic structural unit is that alumina octahedral utilizes the Sauerstoffatom shared to be clipped in the nano level laminate structure formed between two panels silicon-oxy tetrahedron, organic monomer and polymkeric substance can be beneficial to by modification insert between lamella and form stable nano composite material, and only need little filler that mixture just can be made to obtain in physicochemical stability, barrier, mechanical property etc. obviously to strengthen.
Chinese patent CN1546568A reports a kind of polyurethane/molecular sieve matrix material utilizing the molecular sieve of organic modification to prepare as functional reinforcing filler, effectively raise mechanical property and the solvent resistance of urethane, but sieve particle is of a size of micron order, add-on is in the composite relatively high, and heat-insulating property is because this reducing.Chinese patent CN1473876A and CN1398921A has all prepared layered silicate-polyurethane nano composite material using the nano eka-thallium stone organised and the nano imvite organised as filler respectively by melt phase polycondensation, and the dispersion effect of nanoparticle does not reach ideal degree.
The present invention adopts layered silicate to pass through intercalation compounding on above basis, monomer is inserted between the layered silicate lamella that layer inserts agent process, be dispersed in polymkeric substance body, layered silicate-the compound polyurethane material of nanoscale compound is prepared again by in-situ polymerization, and the optimum condition of over-all properties is obtained by controlling inorganics add-on, obtain the over-all properties more preferably compound polyurethane material of stability, thermotolerance, heat preservation property, solve Problems existing in above-mentioned patent preferably.
The information being disclosed in this background technology part is only intended to increase the understanding to general background of the present invention, and should not be regarded as admitting or imply in any form that this information structure has been prior art that persons skilled in the art are known.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide and the invention provides ternary layered silicate-polyurethane nano compound insulating material and in-situ polymerization method for preparing thereof, existing foamed polyurethane lagging material can be solved because can not reach the problem of desirable application requiring without the physical and chemical performance of packing material or the existence of single packing material.
Technical scheme provided by the invention is:
Ternary layered silicate-polyurethane nano compound insulating material, comprises following component by mass percentage: urethane 90-95%, kaolin 2-7% and polynite 2-7%.
As preferably, described kaolin is nano-kaoline; Described polynite is nano level polynite.
Present invention also offers the preparation method of described ternary layered silicate-polyurethane nano compound insulating material, comprise the following steps:
(1) activate: first kaolin or polynite are pulverized, obtain kaolin or montmorillonite particle, in vacuum drying oven after 80 DEG C of dry 4h, with hydrochloric acid soln in mass ratio 1:5 mix, stir process 2h, and in 100 DEG C of dryings, obtain dried activation kaolin or polynite;
(2) prepare intercalation presoma: by dried activation kaolin or polynite and dimethyl sulfoxide (DMSO) in mass ratio 1:3 mix, be placed in grinding in ball grinder 8h, obtain kaolin-dimethyl sulfoxide (DMSO) colloidal solution or the polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation; Dimethyl sulfoxide (DMSO) is added in the kaolin-dimethyl sulfoxide (DMSO) colloidal solution or polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation, the mass ratio of kaolin or polynite and dimethyl sulfoxide (DMSO) is made to reach 1:6, then in 160 DEG C of magnetic agitation reaction 4h, rotating speed is 600r/min, obtains kaolin or montmorillonite intercalation presoma;
(3) intercal type organic nano kaolin or polynite is prepared: by the kaolin that obtains in step (2) or montmorillonite intercalation presoma after 100 DEG C of dryings, mix with the trolamine of its 5 times of total mass numbers, at 170 DEG C of magnetic agitation reaction 2h, rotating speed is 600r/min, then 3 times are rinsed with the dehydrated alcohol that temperature is 60 DEG C, dry in vacuum drying oven at 80 DEG C, to obtain intercal type organic nano kaolin or intercal type organic nano imvite, in loft drier, isolation is dry;
(4) nano material preparation compound polyethers: organic nano kaolin or organic nano imvite are dissolved in polyethers 330; Put into ball mill mixed grinding 3h respectively at after stirred at ambient temperature 1h compound, then respectively at 60 DEG C of water bath sonicator 1h, obtain content and be respectively 10% organic nano kaolin compound polyethers or 10% organic nano imvite compound polyethers;
(5) 10% organic nano kaolin compound polyethers and 10% organic nano imvite compound polyethers is added according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, mixing, obtains homogeneous ternary inorganic materials compound polyethers mixing solutions; Add additive at the ternary inorganic materials compound polyethers mixing solutions prepared, be uniformly mixed, put into 60 DEG C of baking ovens and be incubated 2h, obtain compound polyethers system;
(6) in compound polyethers system, add isocyanic ester according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, after stirring 10s, import room temperature foaming in mould; To be foamed complete after, 80 DEG C of solidification 5h in an oven, the demoulding, i.e. obtained ternary layered silicate-polyurethane nano compound insulating material.
As preferably, the granularity 200-300 order of kaolin and montmorillonite particle in step (1).
As preferably, in step (1), the concentration of hydrochloric acid soln is 5mol/L.
As preferably, in step (2), the rotating speed of ball mill is 110r/min.
As preferably, in step (4), polyethers 330 is 9:1 with the mass ratio of organic nano kaolin or organic nano imvite.
As preferably, the additive described in step (5) is BDO, glycerol, dimethyl methyl phosphonate and stannous octoate.
As preferably, the consumption of described BDO, glycerol, dimethyl methyl phosphonate and stannous octoate is 1/30 of compound polyethers total mass.
As preferably, the speed stirred in step (6) is 600r/min.
Compared with prior art, the present invention has following beneficial effect:
1. ternary layered silicate-polyurethane nano compound insulating material of the present invention has compared to pure inorganic urethane on thermally-stabilised and obviously strengthens, and the binary being better than doping separately inorganic-compound polyurethane material; Ternary layered silicate-polyurethane nano compound insulating material of the present invention is applicable to be directly exposed to the insulation of direct sunlight or the higher equipment of operating temperature or device (such as flat plate solar water heater heat collector and water tank or outdoor large water tank) thermal insulation layer.
2. the raw material output of ternary layered silicate of the present invention-polyurethane nano compound insulating material inorganic nano material used obtains greatly, easily, effectively can reduce the comprehensive cost of product.
3. because nano material specific surface area is very large, be easy in reaction process reunite or crystallization, it is undesirable much to there is inorganic particulate deployment conditions in existing polyurethane inorganic particle composite material, cause the matrix material situation that performance is unexcellent in stability and heat retaining property, preparation method of the present invention successfully solves the problem that the bad dispersibility crystal of nano material in reaction process is easily separated out.
Accompanying drawing explanation
Fig. 1 is that the present invention's ternary layered silicate-polyurethane nano compound insulating material amplifies 40 times of stereoscan photographs;
Fig. 2 is the TG curve of the present invention's ternary layered silicate-polyurethane nano compound insulating material;
The explanation of appended with drawings mark:
The pure urethane of A-; B-95% urethane+5% kaolin; C-95% urethane+5% polynite; D-95% urethane+3% polynite+2% kaolin; E-90% urethane+3% polynite+7% kaolin; The polynite of F-90% urethane+3% kaolin+7%;
The pure urethane of a-; B-95% urethane+5% kaolin; C-95% urethane+5% polynite; D-95% urethane+3% polynite+2% kaolin; E-95% urethane+2% polynite+3% kaolin; The polynite of f-90% urethane+3% kaolin+7%; The polynite of g-90% urethane+7% kaolin+3%.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in detail, but is to be understood that protection scope of the present invention not by the restriction of embodiment.
Clearly represent unless otherwise other, otherwise in whole specification sheets and claims, term " comprise " or its conversion as " comprising " or " including " etc. by be understood to include the element of stating or integral part, and do not get rid of other element or other integral part.
embodiment 1:
Ternary layered silicate-polyurethane nano compound insulating material, comprises following component by mass percentage: urethane 95%, kaolin 2% and polynite 3%; Described kaolin is nano-kaoline; Described polynite is nano level polynite.
Present invention also offers the preparation method of this ternary layered silicate-polyurethane nano compound insulating material, comprise the following steps:
(1) activate: first kaolin or polynite are pulverized, obtain kaolin or montmorillonite particle, granularity 200 order of kaolin and montmorillonite particle; In vacuum drying oven after 80 DEG C of dry 4h, with hydrochloric acid soln in mass ratio 1:5 mix, stir process 2h, and in 100 DEG C of dryings, obtain dried activation kaolin or polynite; The concentration of hydrochloric acid soln is 5mol/L;
(2) prepare intercalation presoma: by dried activation kaolin or polynite and dimethyl sulfoxide (DMSO) in mass ratio 1:3 mix, be placed in grinding in ball grinder 8h, obtain kaolin-dimethyl sulfoxide (DMSO) colloidal solution or the polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation; Dimethyl sulfoxide (DMSO) is added in the kaolin-dimethyl sulfoxide (DMSO) colloidal solution or polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation, the mass ratio of kaolin or polynite and dimethyl sulfoxide (DMSO) is made to reach 1:6, then in 160 DEG C of magnetic agitation reaction 4h, rotating speed is 600r/min, obtains kaolin or montmorillonite intercalation presoma; The rotating speed of ball mill is 110r/min;
(3) intercal type organic nano kaolin or polynite is prepared: by the kaolin that obtains in step (2) or montmorillonite intercalation presoma after 100 DEG C of dryings, mix with the trolamine of its 5 times of total mass numbers, at 170 DEG C of magnetic agitation reaction 2h, rotating speed is 600r/min, then 3 times are rinsed with the dehydrated alcohol that temperature is 60 DEG C, drying in vacuum drying oven at 80 DEG C, will obtain intercal type organic nano kaolin or intercal type organic nano imvite keeps dry;
(4) presoma preparation compound polyethers: polyethers 330 is dissolved and adds organic nano kaolin or organic nano imvite; Put into ball mill mixed grinding 3h respectively at after stirred at ambient temperature 1h compound, then respectively at 60 DEG C of water bath sonicator 1h, obtain content and be respectively 10% organic nano kaolin compound polyethers or 10% organic nano imvite compound polyethers; Polyethers 330 is 9:1 with the mass ratio of organic nano kaolin or organic nano imvite;
(5) 10% organic nano kaolin compound polyethers of 20 weight parts and 10% organic nano imvite compound polyethers of 30 weight parts is added according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, mixing, obtains homogeneous ternary inorganic materials compound polyethers mixing solutions; Add additive at the ternary inorganic materials compound polyethers mixing solutions prepared, be uniformly mixed, put into 60 DEG C of baking ovens and be incubated 2h, obtain compound polyethers system; Described additive is BDO, glycerol, dimethyl methyl phosphonate and stannous octoate; The consumption of described BDO, glycerol, dimethyl methyl phosphonate and stannous octoate is 1/30 of compound polyethers total mass;
(6) in compound polyethers system, add the isocyanic ester of 95 weight parts according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, after stirring 10s, import room temperature foaming in mould; To be foamed complete after, 80 DEG C of solidification 5h in an oven, the demoulding, i.e. obtained ternary layered silicate-polyurethane nano compound insulating material; The speed stirred is 600r/min.
embodiment 2:
Ternary layered silicate-polyurethane nano compound insulating material, comprises following component by mass percentage: urethane 95%, kaolin 3% and polynite 2%; Described kaolin is nano-kaoline; Described polynite is nano level polynite.
Present invention also offers the preparation method of this ternary layered silicate-polyurethane nano compound insulating material, comprise the following steps:
(1) activate: first kaolin or polynite are pulverized, obtain kaolin or montmorillonite particle, granularity 300 order of kaolin and montmorillonite particle; In vacuum drying oven after 80 DEG C of dry 4h, with hydrochloric acid soln in mass ratio 1:5 mix, stir process 2h, and in 100 DEG C of dryings, obtain dried activation kaolin or polynite; The concentration of hydrochloric acid soln is 5mol/L;
(2) prepare intercalation presoma: by dried activation kaolin or polynite and dimethyl sulfoxide (DMSO) in mass ratio 1:3 mix, be placed in grinding in ball grinder 8h, obtain kaolin-dimethyl sulfoxide (DMSO) colloidal solution or the polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation; Dimethyl sulfoxide (DMSO) is added in the kaolin-dimethyl sulfoxide (DMSO) colloidal solution or polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation, the mass ratio of kaolin or polynite and dimethyl sulfoxide (DMSO) is made to reach 1:6, then in 160 DEG C of magnetic agitation reaction 4h, rotating speed is 600r/min, obtains kaolin or montmorillonite intercalation presoma; The rotating speed of ball mill is 110r/min;
(3) intercal type organic nano kaolin or polynite is prepared: by the kaolin that obtains in step (2) or montmorillonite intercalation presoma after 100 DEG C of dryings, mix with the trolamine of its 5 times of total mass numbers, at 170 DEG C of magnetic agitation reaction 2h, rotating speed is 600r/min, then 3 times are rinsed with the dehydrated alcohol that temperature is 60 DEG C, drying in vacuum drying oven at 80 DEG C, will obtain intercal type organic nano kaolin or intercal type organic nano imvite keeps dry;
(4) presoma preparation compound polyethers: polyethers 330 is dissolved and adds organic nano kaolin or organic nano imvite; Put into ball mill mixed grinding 3h respectively at after stirred at ambient temperature 1h compound, then respectively at 60 DEG C of water bath sonicator 1h, obtain content and be respectively 10% organic nano kaolin compound polyethers or 10% organic nano imvite compound polyethers; Polyethers 330 is 9:1 with the mass ratio of organic nano kaolin or organic nano imvite;
(5) 10% organic nano kaolin compound polyethers of 30 weight parts and 10% organic nano imvite compound polyethers of 20 weight parts is added according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, mixing, obtains homogeneous ternary inorganic materials compound polyethers mixing solutions; Add additive at the ternary inorganic materials compound polyethers mixing solutions prepared, be uniformly mixed, put into 60 DEG C of baking ovens and be incubated 2h, obtain compound polyethers system; Described additive is BDO, glycerol, dimethyl methyl phosphonate and stannous octoate; The consumption of described BDO, glycerol, dimethyl methyl phosphonate and stannous octoate is 1/30 of compound polyethers total mass;
(6) in compound polyethers system, add the isocyanic ester of 95 weight parts according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, after stirring 10s, import room temperature foaming in mould; To be foamed complete after, 80 DEG C of solidification 5h in an oven, the demoulding, i.e. obtained ternary layered silicate-polyurethane nano compound insulating material; The speed stirred is 600r/min.
embodiment 3:
Ternary layered silicate-polyurethane nano compound insulating material, comprises following component by mass percentage: urethane 90%, kaolin 3% and polynite 7%; Described kaolin is nano-kaoline; Described polynite is nano level polynite.
Present invention also offers the preparation method of this ternary layered silicate-polyurethane nano compound insulating material, comprise the following steps:
(1) activate: first kaolin or polynite are pulverized, obtain kaolin or montmorillonite particle, granularity 220 order of kaolin and montmorillonite particle; In vacuum drying oven after 80 DEG C of dry 4h, with hydrochloric acid soln in mass ratio 1:5 mix, stir process 2h, and in 100 DEG C of dryings, obtain dried activation kaolin or polynite; The concentration of hydrochloric acid soln is 5mol/L;
(2) prepare intercalation presoma: by dried activation kaolin or polynite and dimethyl sulfoxide (DMSO) in mass ratio 1:3 mix, be placed in grinding in ball grinder 8h, obtain kaolin-dimethyl sulfoxide (DMSO) colloidal solution or the polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation; Dimethyl sulfoxide (DMSO) is added in the kaolin-dimethyl sulfoxide (DMSO) colloidal solution or polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation, the mass ratio of kaolin or polynite and dimethyl sulfoxide (DMSO) is made to reach 1:6, then in 160 DEG C of magnetic agitation reaction 4h, rotating speed is 600r/min, obtains kaolin or montmorillonite intercalation presoma; The rotating speed of ball mill is 110r/min;
(3) intercal type organic nano kaolin or polynite is prepared: by the kaolin that obtains in step (2) or montmorillonite intercalation presoma after 100 DEG C of dryings, mix with the trolamine of its 5 times of total mass numbers, at 170 DEG C of magnetic agitation reaction 2h, rotating speed is 600r/min, then 3 times are rinsed with the dehydrated alcohol that temperature is 60 DEG C, drying in vacuum drying oven at 80 DEG C, will obtain intercal type organic nano kaolin or intercal type organic nano imvite keeps dry;
(4) presoma preparation compound polyethers: polyethers 330 is dissolved and adds organic nano kaolin or organic nano imvite; Put into ball mill mixed grinding 3h respectively at after stirred at ambient temperature 1h compound, then respectively at 60 DEG C of water bath sonicator 1h, obtain content and be respectively 10% organic nano kaolin compound polyethers or 10% organic nano imvite compound polyethers; Polyethers 330 is 9:1 with the mass ratio of organic nano kaolin or organic nano imvite;
(5) 10% organic nano kaolin compound polyethers of 30 weight parts and 10% organic nano imvite compound polyethers of 70 weight parts is added according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, mixing, obtains homogeneous ternary inorganic materials compound polyethers mixing solutions; Add additive at the ternary inorganic materials compound polyethers mixing solutions prepared, be uniformly mixed, put into 60 DEG C of baking ovens and be incubated 2h, obtain compound polyethers system; Described additive is BDO, glycerol, dimethyl methyl phosphonate and stannous octoate; The consumption of described BDO, glycerol, dimethyl methyl phosphonate and stannous octoate is 1/30 of compound polyethers total mass;
(6) in compound polyethers system, add the isocyanic ester of 90 weight parts according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, after stirring 10s, import room temperature foaming in mould; To be foamed complete after, 80 DEG C of solidification 5h in an oven, the demoulding, i.e. obtained ternary layered silicate-polyurethane nano compound insulating material; The speed stirred is 600r/min.
embodiment 4:
Ternary layered silicate-polyurethane nano compound insulating material, comprises following component by mass percentage: urethane 90%, kaolin 7% and polynite 3%; Described kaolin is nano-kaoline; Described polynite is nano level polynite.
Present invention also offers the preparation method of this ternary layered silicate-polyurethane nano compound insulating material, comprise the following steps:
(1) activate: first kaolin or polynite are pulverized, obtain kaolin or montmorillonite particle, granularity 250 order of kaolin and montmorillonite particle; In vacuum drying oven after 80 DEG C of dry 4h, with hydrochloric acid soln in mass ratio 1:5 mix, stir process 2h, and in 100 DEG C of dryings, obtain dried activation kaolin or polynite; The concentration of hydrochloric acid soln is 5mol/L;
(2) prepare intercalation presoma: by dried activation kaolin or polynite and dimethyl sulfoxide (DMSO) in mass ratio 1:3 mix, be placed in grinding in ball grinder 8h, obtain kaolin-dimethyl sulfoxide (DMSO) colloidal solution or the polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation; Dimethyl sulfoxide (DMSO) is added in the kaolin-dimethyl sulfoxide (DMSO) colloidal solution or polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation, the mass ratio of kaolin or polynite and dimethyl sulfoxide (DMSO) is made to reach 1:6, then in 160 DEG C of magnetic agitation reaction 4h, rotating speed is 600r/min, obtains kaolin or montmorillonite intercalation presoma; The rotating speed of ball mill is 110r/min;
(3) intercal type organic nano kaolin or polynite is prepared: by the kaolin that obtains in step (2) or montmorillonite intercalation presoma after 100 DEG C of dryings, mix with the trolamine of its 5 times of total mass numbers, at 170 DEG C of magnetic agitation reaction 2h, rotating speed is 600r/min, then 3 times are rinsed with the dehydrated alcohol that temperature is 60 DEG C, drying in vacuum drying oven at 80 DEG C, will obtain intercal type organic nano kaolin or intercal type organic nano imvite keeps dry;
(4) presoma preparation compound polyethers: polyethers 330 is dissolved and adds organic nano kaolin or organic nano imvite; Put into ball mill mixed grinding 3h respectively at after stirred at ambient temperature 1h compound, then respectively at 60 DEG C of water bath sonicator 1h, obtain content and be respectively 10% organic nano kaolin compound polyethers or 10% organic nano imvite compound polyethers; Polyethers 330 is 9:1 with the mass ratio of organic nano kaolin or organic nano imvite;
(5) 10% organic nano kaolin compound polyethers of 70 weight parts and 10% organic nano imvite compound polyethers of 30 weight parts is added according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, mixing, obtains homogeneous ternary inorganic materials compound polyethers mixing solutions; Add additive at the ternary inorganic materials compound polyethers mixing solutions prepared, be uniformly mixed, put into 60 DEG C of baking ovens and be incubated 2h, obtain compound polyethers system; Described additive is BDO, glycerol, dimethyl methyl phosphonate and stannous octoate; The consumption of described BDO, glycerol, dimethyl methyl phosphonate and stannous octoate is 1/30 of compound polyethers total mass;
(6) in compound polyethers system, add the isocyanic ester of 90 weight parts according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, after stirring 10s, import room temperature foaming in mould; To be foamed complete after, 80 DEG C of solidification 5h in an oven, the demoulding, i.e. obtained ternary layered silicate-polyurethane nano compound insulating material; The speed stirred is 600r/min.
the performance analysis of the present invention's ternary layered silicate-polyurethane nano compound insulating material:
Ternary layered silicate-polyurethane nano the compound insulating material prepared by embodiment 1-4 adopts U.S. TGAQ50 thermogravimetric analyzer (TG data+TG curve), HITACHS-3400N scanning electron microscope (scanning spectra) etc. to characterize the test that different doped series sample has carried out thermogravimetric microtexture aspect system respectively, and test result is in table 1, Fig. 1 and Fig. 2.
The ternary layered silicate of table 1 the present invention-polyurethane nano compound insulating material thermogravimetric analysis (TG) data
As can be seen from Table 1, the initial decomposition peak temperature of ternary layered silicate-polyurethane nano compound insulating material of the present invention is all apparently higher than contrast 1, contrast 2, contrast 3; 25% decomposition temperature is also apparently higher than contrast 1, contrast 2, contrast 3.
As can be seen from Figure 1, in the microtexture of system, twoly mix that to play be synergitic beneficial effect.Compared to singly mixing system, the doping of two kinds of nano materials does not make pore structure be deteriorated; When total doping content is 5%, it is little that foam structure and 5% singly mixes system difference; And along with the increase of total doping content, foam structure has the trend increased further; Relative to singly mixing for kaolin clay system, polynite+kaolin clay system have evenly foam structure; In three-component compound system, the structure of polyurethane matrix material is also very complete simultaneously, and pore structure and size are also comparatively even.
As can be seen from table 1 and Fig. 2, although singly mix compound system (95% urethane+5% polynite; 95% urethane+5% kaolin) also improve significantly in heat decomposition curve, but twoly mix compound system (95% urethane+3% polynite+2% kaolin; 95% urethane+2% polynite+3% kaolin) then under the constant condition of total doping content, obtain higher heat decomposition temperature.
In sum, ternary layered silicate-polyurethane nano compound insulating material of the present invention has compared to pure inorganic urethane on thermally-stabilised and obviously strengthens, and the binary being better than doping separately inorganic-compound polyurethane material; Ternary layered silicate-polyurethane nano compound insulating material of the present invention is applicable to be directly exposed to the insulation of direct sunlight or the higher equipment of operating temperature or device (such as flat plate solar water heater heat collector and water tank or outdoor large water tank) thermal insulation layer, has good market outlook.
The aforementioned description to concrete exemplary of the present invention is to illustrate and the object of illustration.These descriptions not want the present invention to be defined as disclosed precise forms, and obviously, according to above-mentioned instruction, can much change and change.The object selected exemplary embodiment and describe is to explain certain principles of the present invention and practical application thereof, thus those skilled in the art can be realized and utilize various different exemplary of the present invention and various different selection and change.Scope of the present invention is intended to limited by claims and equivalents thereof.
Claims (10)
1. ternary layered silicate-polyurethane nano compound insulating material, is characterized in that, comprises following component by mass percentage: urethane 90-95%, kaolin 2-7% and polynite 2-7%.
2. ternary layered silicate-polyurethane nano compound insulating material according to claim 1, is characterized in that: described kaolin is nano-kaoline; Described polynite is nano level polynite.
3. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 1 and 2, is characterized in that, comprise the following steps:
(1) activate: first kaolin or polynite are pulverized, obtain kaolin or montmorillonite particle, in vacuum drying oven after 80 DEG C of dry 4h, with hydrochloric acid soln in mass ratio 1:5 mix, stir process 2h, and in 100 DEG C of dryings, obtain dried activation kaolin or polynite;
(2) prepare intercalation presoma: by dried activation kaolin or polynite and dimethyl sulfoxide (DMSO) in mass ratio 1:3 mix, be placed in grinding in ball grinder 8h, obtain kaolin-dimethyl sulfoxide (DMSO) colloidal solution or the polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation; Dimethyl sulfoxide (DMSO) is added in the kaolin-dimethyl sulfoxide (DMSO) colloidal solution or polynite-dimethyl sulfoxide (DMSO) colloidal solution of part intercalation, the mass ratio of kaolin or polynite and dimethyl sulfoxide (DMSO) is made to reach 1:6, then in 160 DEG C of magnetic agitation reaction 4h, rotating speed is 600r/min, obtains kaolin or montmorillonite intercalation presoma;
(3) intercal type organic nano kaolin or polynite is prepared: by the kaolin that obtains in step (2) or montmorillonite intercalation presoma after 100 DEG C of dryings, mix with the trolamine of its 5 times of total mass numbers, at 170 DEG C of magnetic agitation reaction 2h, rotating speed is 600r/min, then 3 times are rinsed with the dehydrated alcohol that temperature is 60 DEG C, dry in vacuum drying oven at 80 DEG C, to obtain intercal type organic nano kaolin or intercal type organic nano imvite, in loft drier, isolation is dry;
(4) nano material preparation compound polyethers: organic nano kaolin or organic nano imvite are dissolved in polyethers 330; Put into ball mill mixed grinding 3h respectively at after stirred at ambient temperature 1h compound, then respectively at 60 DEG C of water bath sonicator 1h, obtain content and be respectively 10% organic nano kaolin compound polyethers or 10% organic nano imvite compound polyethers;
(5) 10% organic nano kaolin compound polyethers and 10% organic nano imvite compound polyethers is added according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, mixing, obtains homogeneous ternary inorganic materials compound polyethers mixing solutions; Add additive at the ternary inorganic materials compound polyethers mixing solutions prepared, be uniformly mixed, put into 60 DEG C of baking ovens and be incubated 2h, obtain compound polyethers system;
(6) in compound polyethers system, add isocyanic ester according to the formula rate of ternary layered silicate-polyurethane nano compound insulating material, after stirring 10s, import room temperature foaming in mould; To be foamed complete after, 80 DEG C of solidification 5h in an oven, the demoulding, i.e. obtained ternary layered silicate-polyurethane nano compound insulating material.
4. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 3, is characterized in that, the granularity 200-300 order of kaolin and montmorillonite particle in step (1).
5. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 3, is characterized in that, in step (1), the concentration of hydrochloric acid soln is 5mol/L.
6. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 3, is characterized in that, in step (2), the rotating speed of ball mill is 110r/min.
7. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 3, is characterized in that, in step (4), polyethers 330 is 9:1 with the mass ratio of organic nano kaolin or organic nano imvite.
8. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 3, is characterized in that, the additive described in step (5) is BDO, glycerol, dimethyl methyl phosphonate and stannous octoate.
9. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 7, it is characterized in that, the consumption of described BDO, glycerol, dimethyl methyl phosphonate and stannous octoate is 1/30 of compound polyethers total mass.
10. the preparation method of ternary layered silicate-polyurethane nano compound insulating material according to claim 4, is characterized in that, the speed stirred in step (6) is 600r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953532.1A CN105418877A (en) | 2015-12-18 | 2015-12-18 | Ternary phyllosilicate-polyurethane nano-composite thermal insulation material and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510953532.1A CN105418877A (en) | 2015-12-18 | 2015-12-18 | Ternary phyllosilicate-polyurethane nano-composite thermal insulation material and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105418877A true CN105418877A (en) | 2016-03-23 |
Family
ID=55497453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510953532.1A Pending CN105418877A (en) | 2015-12-18 | 2015-12-18 | Ternary phyllosilicate-polyurethane nano-composite thermal insulation material and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105418877A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619464A (en) * | 2017-09-26 | 2018-01-23 | 南宁可煜能源科技有限公司 | Solar insulated water tank polyurethane composite thermal insulation material |
| CN108484865A (en) * | 2018-04-26 | 2018-09-04 | 汤广金 | Heat-insulation and heat-preservation free-floride foamed material and preparation method thereof |
| CN108586704A (en) * | 2018-04-26 | 2018-09-28 | 汤广金 | Insulation aluminium section bar and preparation method thereof |
| US12025258B2 (en) | 2018-12-19 | 2024-07-02 | Dow Global Technologies Llc | Bonded multilayer article |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307129A (en) * | 2007-05-17 | 2008-11-19 | 宁波星箭航天机械厂 | Polyurethane/organic montmorillonite nano composite material and method for preparing same |
| CN101544853A (en) * | 2009-04-23 | 2009-09-30 | 兰州大学 | Intercalated organic nano kaolin, preparation thereof and application in preparing polyurethane nano-composite foam material |
| CN102002141A (en) * | 2010-11-19 | 2011-04-06 | 安徽大学 | Preparation method of polyurethane-nano kaolin composite material |
-
2015
- 2015-12-18 CN CN201510953532.1A patent/CN105418877A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307129A (en) * | 2007-05-17 | 2008-11-19 | 宁波星箭航天机械厂 | Polyurethane/organic montmorillonite nano composite material and method for preparing same |
| CN101544853A (en) * | 2009-04-23 | 2009-09-30 | 兰州大学 | Intercalated organic nano kaolin, preparation thereof and application in preparing polyurethane nano-composite foam material |
| CN102002141A (en) * | 2010-11-19 | 2011-04-06 | 安徽大学 | Preparation method of polyurethane-nano kaolin composite material |
Non-Patent Citations (4)
| Title |
|---|
| 冯威: "硬质聚氨酯泡沫塑料/层状硅酸盐复合材料的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 张书华等编著: "《高性能电缆材料及其应用技术》", 30 November 2015 * |
| 李学强: "高岭土/有机插层纳米复合物研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
| 赵菲: "聚氨酯/纳米层状蒙脱土复合材料", 《第三届全国橡胶助剂生产及应用技术交流会论文集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619464A (en) * | 2017-09-26 | 2018-01-23 | 南宁可煜能源科技有限公司 | Solar insulated water tank polyurethane composite thermal insulation material |
| CN108484865A (en) * | 2018-04-26 | 2018-09-04 | 汤广金 | Heat-insulation and heat-preservation free-floride foamed material and preparation method thereof |
| CN108586704A (en) * | 2018-04-26 | 2018-09-28 | 汤广金 | Insulation aluminium section bar and preparation method thereof |
| CN108586704B (en) * | 2018-04-26 | 2021-05-07 | 广东金华海铝业有限公司 | Heat-preservation and heat-insulation aluminum profile and preparation method thereof |
| CN108484865B (en) * | 2018-04-26 | 2021-09-07 | 江门市健楠包装材料有限公司 | Thermal insulation fluorine-free foam material and preparation method thereof |
| US12025258B2 (en) | 2018-12-19 | 2024-07-02 | Dow Global Technologies Llc | Bonded multilayer article |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Modification of diatomite with melamine coated zeolitic imidazolate framework-8 as an effective flame retardant to enhance flame retardancy and smoke suppression of rigid polyurethane foam | |
| Nabipour et al. | Zeolitic imidazolate framework-8/polyvinyl alcohol hybrid aerogels with excellent flame retardancy | |
| CN105418877A (en) | Ternary phyllosilicate-polyurethane nano-composite thermal insulation material and preparing method thereof | |
| CN107325328B (en) | A kind of preparation method of graphene/silicon dioxide compound particle | |
| CN111039295B (en) | Method for preparing silicon dioxide aerogel and self-hydrophobic silicon dioxide aerogel heat-insulating felt pad by one-step method | |
| CN102898778A (en) | Preparation method for melamine formaldehyde resin closed-cell foam | |
| CN103937234A (en) | Thermal conductive plastic applying modified carbon material, and preparation method thereof | |
| CN104998674A (en) | Silicate clay-carbon nitride composite material of multilevel structure and preparation method of silicate clay-carbon nitride composite material | |
| US20160208069A1 (en) | Thermal Insulation Expandable Polystyrene Particles and Method of Preparing the Same | |
| CN113999534B (en) | Graphene ultraviolet-resistant flame-retardant synergist and preparation method thereof | |
| Sun et al. | Fabrication of flame-retardant and smoke-suppressant isocyanate-based polyimide foam modified by silica aerogel thermal insulation and flame protection layers | |
| CN105885313B (en) | Resin cross-linking polyvinyl alcohol aeroge and its preparation method and application | |
| CN113338458A (en) | Flame-retardant EPS insulation board and preparation method thereof | |
| CN106832071A (en) | The preparation method of polystyrene and the compound XPS plate material of aerosil | |
| CN102618016A (en) | Light-transparent heat insulating film, its preparation method and application | |
| CN101157799A (en) | Polyaniline/nano graphite lamella/Eu[3+] nano film material and method for making same | |
| CN114031817B (en) | COFs modified ammonium polyphosphate flame retardant, preparation method and application thereof, and flame-retardant epoxy resin | |
| CN108752722B (en) | Antistatic EVA foam composite material and preparation method thereof | |
| CN112662101B (en) | Polyvinyl alcohol-organic phosphonic acid @ graphene-based membrane, multilayer film and preparation method thereof | |
| KR101254425B1 (en) | Graphene film having graphene oxide/poly vinyl alcohol composite and manufacturing method of the same | |
| CN110127670A (en) | A kind of graphene three-dimensional structure aeroge hydrophobic material | |
| CN110294469A (en) | A kind of three-dimensional graphene composite material and preparation method thereof | |
| CN108539149A (en) | A kind of graphene composite nitrogen, oxygen codope biomass carbon material and preparation method thereof | |
| CN116284952B (en) | Preparation method of foaming polypropylene based on supercritical carbon dioxide | |
| Wang et al. | Study of preparation and properties of fire-retardant melamine formaldehyde resin foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160323 |
|
| RJ01 | Rejection of invention patent application after publication |