CN101633197A - Method for producing energy-saving scagliola containing microencapsulated phase change materials - Google Patents

Method for producing energy-saving scagliola containing microencapsulated phase change materials Download PDF

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CN101633197A
CN101633197A CN200910041545A CN200910041545A CN101633197A CN 101633197 A CN101633197 A CN 101633197A CN 200910041545 A CN200910041545 A CN 200910041545A CN 200910041545 A CN200910041545 A CN 200910041545A CN 101633197 A CN101633197 A CN 101633197A
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phase change
stone
weight
energy
saving
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CN101633197B (en
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袁文辉
陈华荣
董钊行
李莉
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0046—Polymers chosen for their physico-chemical characteristics added as monomers or as oligomers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00439—Physico-chemical properties of the materials not provided for elsewhere in C04B2111/00
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone
    • C04B2111/545—Artificial marble

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

The invention discloses a method for producing energy-saving scagliola containing microencapsulated phase change materials. The method comprises the following steps: mixing microencapsulated pulverulent bodies, unsaturated polyester resin with quartz powder according to a proportion of 0.6-3:0.2-0.5:1; adding the mixture into man-made stone substrate according to the used category, adding pigment into bed charge, and adding a curing agent, namely ethyl methyl ketone peroxide, and an accelerator, namely cobalt iso-octoate at the same time; putting stone the stone substrate containing microencapsulated phase change materials into a vacuum forming mould for forming through vibration, and then printing patterns on the surface of stone materials according to specific needs to obtain finished product. Composite stone materials produced by using the method of the invention have similar bending strength, abrasion resistance, Mohs hardness and the like as ordinary stone materials, and have favorable characteristics of heat storage and dispersion because of the microencapsulated phase change materials which are added into raw materials, thus adjustable indoor temperature favorably to realize the energy-saving effect; therefore, the composite stone materials can be widely used as modern building decorative materials.

Description

A kind of preparation method of energy-saving artificial marble of material containing micro-capsule phase change
Technical field:
The present invention relates to microencapsulated phase change material applied technical field in chemical industry, stone industries and the building industry, specifically is the preparation method of the energy-saving artificial marble of material containing micro-capsule phase change.
Technical background:
Microcapsules technology is a kind of technology that solid, liquid or gas is coated the formation fine particle with filmogen.Microcapsules be exactly with certain material with some macromolecular compound or inorganic compound, adopt machinery or chemical method to coat, this material is protected, avoid external influence and go bad the particulate that is released in due course.
(Micro-encapsulated Phase Change Materials, research MPCM) is microcapsules technology to be applied in the phase-change material and the new research field that forms to microencapsulated phase change material.MPCM is formed by inner nuclear material and sheathing material two parts, its phase transition temperature scope is between-50～150 ℃, determine its heat absorption and exothermicity according to the phase transition temperature of inner nuclear material, the kernel of MPCM is that solid-liquid phase becomes material, it is the core of MPCM, will directly influence the storage heat release and the temperature-control performance of product.At present, the solid-liquid phase that can be used as the microcapsules kernel becomes material crystalline hydrate salt, eutectic hydrated salt, linear paraffin, paraffin class, fatty acid, polyethylene glycol etc., and wherein crystalline hydrate salt and paraffin class are comparatively commonly used.Sheathing material is for phase-change material provides stable phase transformation space, mainly plays the effect of protection and sealing phase-change material.Sheathing material is to the performance important influence of microcapsules, and different applications has different requirements to sheathing material.Sheathing material is often selected macromolecular material for use, and available have polyethylene, polystyrene, polyureas, polyamide, epoxy resin, Lauxite, a melamine formaldehyde resin etc.
MPCM has not only solved the stability of inorganic phase-changing material and the thermal conductivity and the Volume Changes problem of organic phase change material, but also has simplified the use technology of phase-change material, has reduced use cost.MPCM has good heat retention characteristic and temperature-control performance, but the field of extensive use is a lot, can also mix with various macromolecular materials to constitute the more superior composite high-molecular phase-change material of performance, has widened the application of traditional phase-change material.MPCM in some practical application area be used for the temporary transient variations in temperature of balance with storage power.Not only in electron trade, auto industry, textile industry but also in building industry and processing of stone industry, also obtained widely using.
Energy-saving artificial stone of the present invention is that artificial stone and microcapsule phase-change thermal storage material is compound, make novel artificial stone have the function of automatic adjusting temperature, using interfacial polymerization and situ aggregation method that a series of paraffin compounds are carried out encapsulated the preparation wraps up fully, permeability is lower, the double shell microcapsule that can use repeatedly, regulate indoor temperature by the microcapsule phase-change thermal storage artificial stone simultaneously, reduce fluctuation, energy savings in a large number, the phase-change accumulation energy construction material is as a kind of novel building functional material, energy-conservation, there is good prospects for application the energy storage aspect.Recently the researcher of Freiburg, Germany Fu Langfei solar energy system research institute and BASF AG of Konzern utilizes the liquid paraffin can these characteristics of accumulation of heat, utilizes microcapsules technology that paraffin is coated, and adds then to be applied to building materials in the plaster.This building materials can absorb heat, make paraffin molecule fusion, and it is when solidifying, and heat can discharge again.U.S. Suntek ResearchAssociate company succeeds in developing the heat accumulation wall block, and it is suspended in phase-change material in the concrete segment, as constant temperature heat accumulation building element.Its preparation method is that air in the building block is taken away, fills the phase-change material of melting state then, coats confining bed more outside.
The microcapsules heat storage phase-changing material provides a kind of effective way that increases the building comfort level and cut down the consumption of energy, reduce the environment negative effect with rationally utilizing combining of solar energy.The phase-change accumulation energy construction material is as a kind of novel building functional material, aspect energy-conservation, energy storage good prospects for application arranged.
Summary of the invention:
The object of the present invention is to provide the preparation method of construction materials such as a kind of floor tile that contains microencapsulated phase change material that is suitable for building industry or walltile.This method technology is simple, the low and environmental protection of cost, and give stone material good neither endothermic nor exothermic performance, and make indoor environment reach effect cool in summer and warm in winter, improve the human comfort that is under the variation of ambient temperature.
For realizing purpose of the present invention, adopt following technical scheme:
A kind of preparation method of the energy-saving artificial marble of material containing micro-capsule phase change comprises the steps:
(1) use interfacial polymerization and situ aggregation method that a series of paraffin compounds are carried out the encapsulated double shell microcapsule that parcel is complete, permeability is lower, can use repeatedly for preparing simultaneously;
(2) microcapsules powder, the Binder Materials (182 unsaturated polyester resin) that under the normal temperature (1) is made mixed according to 1: 0.5～2: 4～10 ratio with silica flour;
(3) according to used category (2) gained mixture is added in the artificial stone base material according to certain ratio, and select suitable pigment to add in the bed material, add suitable curing agent methyl ethyl ketone peroxide and promoter cobalt iso-octoate simultaneously;
(4) by the mould molding technology, the stone material base-material that will contain microencapsulated phase change material is put into the vacuum forming machine mould through the vibration moulding, and gets finished product according to concrete needs behind the stone surface printing pattern.
Microencapsulated phase change material content is 10%～35% in the affiliated finished product, and described microencapsulated phase change material powder is meant that microcapsules kernel phase transition temperature is-50～150 ℃ micron or a nano-powder material.
Useful is that the energy-saving artificial marble of described material containing micro-capsule phase change is mainly used in construction materials such as walltile, floor tile, curtain wall.
Useful is that Binder Materials is 182 unsaturated polyester resins in the preparation process step (3) of the energy-saving artificial marble of described material containing micro-capsule phase change.
Wherein the construction material of various different use occasions carries out in different moulds in the step (4), and the pattern on surface also can the moulding by changing mould.
Described double shell microcapsule phase change material laboratory preparation method is as follows:
(1) emulsification of core: 1.5～5.4 parts of TDI are total to molten formation core solution with 55～85 parts of n-octadecane/paraffin under 60～70 ℃ condition; The adding of core solution is dissolved with in the deionized water of 0.1%～0.3% protecting colloid hydroxyethylcellulose and 1.2%～1.8% emulsifying agent, and emulsification 10～20min under the condition of 5000～9000rpm forms the core emulsion;
(2) hypostracum coats: drip 2.1～4.8 part of 45～65% (weight) ethylenediamine (EDA) aqueous solution under 300～400rpm, 60～70 ℃ of conditions in the core emulsion that makes, after dropwising, reacted 1～2 hour, and obtained the microcapsule emulsion of polyureas parcel;
(3) preparation of outer shell prepolymer: 6.0～10.8 parts of melamines and 10.8～24.6 part of 37% formalin are joined in 40～50 parts of deionized waters, with mass concentration 90% triethanolamine adjust pH to 7～8, be warming up to 70～75 ℃, stir, to the transparent carbamide performed polymer that gets of solution;
(4) outer shell coats: the melamine formaldehyde resin performed polymer is added in the microcapsule emulsion of step (2) preparation, with mass concentration 10% citric acid solution adjust pH to 5～6, under 70～75 ℃ of conditions, under the condition of 300～400rpm, reacted 1～2 hour, cooling, discharging promptly gets microcapsule solution, more after filtration, wash, be drying to obtain the microcapsules powder.
The consumption of above-mentioned all substances is in parts by weight.
Described emulsifying agent is the anion emulsifier Sodium Polyacrylate: the nonionic emulsifier polypropylene glycol is 1: 1～2.3 compound emulsifying agent.
Beneficial effect of the present invention is as follows:
(1) the present invention adopts microencapsulated phase change material under phase transition temperature arbitrarily as raw material, and production technology is simple, safety, efficient, and material external form and surperficial moulding pattern thereof can be selected voluntarily, and this technology does not have any harm influence to human body and surrounding environment.
(2) the present invention solves the fatigue problem of phase-change material by synthetic double shells microcapsule, makes construction material have long service life.
(3) phase-change material that makes of the present invention can make its phase transition temperature be adjusted to comfortable 16～25 ℃ of human body sensory, and the phase-change material that makes has higher latent heat of phase change, heat absorption capacity is good, can be widely used in all kinds of construction materials, as walltile, floor tile, curtain wall etc.
(4) stone material for building that makes of the present invention can play good temperature adjustment energy saving effect, in hot summer heat is stored in the phase-change material, reduces indoor temperature; The cold winter then will before the heat that stores discharge, to improve indoor temperature.
Description of drawings:
Fig. 1 is the DSC curve map of n-octadecane microcapsules.
The specific embodiment:
The present invention will be further described below in conjunction with example and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1:
The preparation double shell microcapsule phase change material:
(1) emulsification of core: 3.5 parts of TDI are total to molten formation core solution with 60 parts of n-octadecanes under 65 ℃ condition; Core solution is added in 20 parts of the deionized waters being dissolved with 0.1% (weight) protecting colloid hydroxyethylcellulose and 1.8% (weight) emulsifying agent, and emulsification 15min under the condition of 9000rpm forms the core emulsion;
(2) hypostracum coats: drip 3 part of 55% (weight) ethylenediamine (EDA) aqueous solution in the core emulsion under 300rpm, 65 ℃ of conditions, after dropwising, reacted 1.5 hours, obtain the microcapsule emulsion of polyureas parcel;
(3) preparation of outer shell prepolymer: get and contain 13.5 parts of the deionized waters that 7% (weight) melamine and 15% (weight) concentration are the formalin of 37% (weight), it with mass concentration 90% triethanolamine adjust pH to 7.5, be warming up to 70 ℃, stir, to the transparent carbamide performed polymer that gets of solution;
(4) outer shell coats: the melamine formaldehyde resin performed polymer is added in the microcapsule emulsion of step (2) preparation, it with mass concentration 10% citric acid solution adjust pH to 5.5, under 70 ℃ of conditions, reaction is 2 hours under the condition of 300rpm, cooling, discharging promptly gets microcapsule solution, more after filtration, wash, be drying to obtain the microcapsules powder.
Described emulsifying agent is the compound emulsifying agent that contains 60 weight portion anion emulsifier Sodium Polyacrylates and 40 weight portion nonionic emulsifier polypropylene glycols.
The umber of above-mentioned all substances is in parts by weight.
Fig. 1 is for being core with the n-octadecane, and EDA and TDI are the inner casing material, the DSC curve map of the microencapsulated phase change material that the carbamide performed polymer makes for the shell material, and its DSC curve adopts U.S. MDSC 2910, and TAInstruments type DSC tester is measured.
The value of fuel factor (thermal discharge and caloric receptivity) is directly proportional with the peak area of DSC curve, is the method that extensively adopts by curve calculated by peak area fuel factor value, and its relational expression can be expressed as:
H＝K·A
H: heat;
A: the area at curve peak;
K: instrumental correction coefficient (asking calculation) by the standard substance of measuring known fuel factor value
Cut paper weighing method or planimeter etc. are adopted in the measuring and calculating of peak area in early days.All pass through data processing equipment at present, adopt the computer measuring and calculating, and on curve, directly be converted into Δ H demonstration record.Endothermic peak and exothermic peak are the caloric receptivity and the thermal discharge of phase-change material respectively among Fig. 1 with the area of baseline formation closed area, and as seen from the figure, microencapsulated phase change material is 30.443 ℃ in the endothermic peak temperature, and total caloric receptivity is 183.3J/g; Falling the thermal peak temperature is 22.463 ℃, and total thermal discharge is 180.8J/g.This microencapsulated phase change material heat absorption exothermicity is good.Choosing granularity is 2～7 μ m, and heat absorption is carried out the production and processing of stone material with exothermicity microencapsulated phase change material powder as shown in Figure 1.
Take by weighing raw material by following proportioning and produce red floor tile:
20 kilograms of method for preparing microencapsulated phase change material powders, 6 kilograms of 182 unsaturated polyester resins (Shenyang Ward chemistry Co., Ltd), 0.5 kilogram of 335 saturated resin (Shenyang Ward chemistry Co., Ltd), 30 kilograms of silica flours, 80 kilograms of marble particles, RTV organosilicon 0.1 kilogram of (Dongguan City Ruo Lin trade Co., Ltd), 0.01 kilogram of cobalt iso-octoate, 0.1 kilogram of methyl ethyl ketone peroxide, 0.1 kilogram of iron oxide red.Above-mentioned powder material is placed in the refiner, add 20 kilograms in water, the mixing and stirring form slurry; Be positioned in the A/ZKX-1 vacuum forming machine mould slurry fixed-type; The blank that above-mentioned make-up machine makes is heated to 60 ℃, treat to carry out the demoulding, maintenance after the blank cooled and solidified, obtain the square stock that specification is 0.7m * 0.7m * 2.5m; With gang saw square stock is cut into the hair plates that thickness is 15mm, dry; Repair plate face pore with 182 unsaturated polyester resins (Shenyang Ward chemistry Co., Ltd) strike-through, handle promptly getting the red floor tile that thickness is 12mm through fine-grinding and polishing.The contrast of every performance indications of product and the red floor tile of wine produced with Guangdong Province Yunfu Yueyun New Stone Material Co., Ltd. existing production technology thereof sees table 1 for details.
The energy-saving red floor tile performance indications of table 1 material containing micro-capsule phase change
Performance Test result Prior art
The wear-resisting rate/(g/cm of the compressive strength of the bending strength of the thermal discharge of quantity of heat storage/(J/g)/(J/g)/(MPa)/(MPa) 3) the linear heat of Mohs' hardness is swollen/(g/ ℃) ??150.6 ??147.8 ??20 ??120 ??3×10 -3??4 ??1～4×10 -5 ??70.5 ??61.4 ??19.8 ??118 ??3.1×10 -3??4 ??1～4×10 -5
By being compared with the prior art as can be known, by being compared with the prior art as can be known, its heat accumulation thermal discharge of novel stone material of the present invention's development all exceeds nearly 80J/g than prior art, the novel stone material of the present invention's development has better heat accumulation and heat release function, can be good at regulating indoor temperature, reach purpose of energy saving.Other performance parameter of product lateral bending Qu Qiangdu and compressive strength strictly according to the facts slightly is better than prior art, and wear-resisting rate, Mohs' hardness and linear expansion coefficient etc. are suitable with prior art.
Embodiment 2:
The preparation double shell microcapsule phase change material:
(1) emulsification of core: 3 parts of TDI are total to molten formation core solution with 65 parts of positive n-octadecanes under 70 ℃ condition; Core solution is added in 20 parts of the deionized waters being dissolved with 0.2% (weight) protecting colloid hydroxyethylcellulose and 1.7% (weight) emulsifying agent emulsification 20min under the condition of 9000rpm, formation core emulsion;
(2) hypostracum coats: drip 3 part of 50% (weight) ethylenediamine (EDA) aqueous solution in emulsion under 300rpm, 70 ℃ of conditions, after dropwising, reacted 1.5 hours, obtain the microcapsule emulsion of polyureas parcel;
(3) preparation of outer shell prepolymer: get and contain 12 parts of the deionized waters that 7% (weight) melamine and 15% (weight) concentration are the formalin of 37% (weight), it with mass concentration 90% triethanolamine adjust pH to 7.5, be warming up to 70 ℃, stir, to the transparent carbamide performed polymer that gets of solution;
(4) outer shell coats: the melamine formaldehyde resin performed polymer is added in the microcapsule emulsion of step (2) preparation, it with mass concentration 10% citric acid solution adjust pH to 5.5, under 70 ℃ of conditions, reaction is 2 hours under the condition of 300rpm, cooling, discharging promptly gets microcapsule solution, more after filtration, wash, be drying to obtain the microcapsules powder.
Described emulsifying agent is the compound emulsifying agent that contains 65 weight portion anion emulsifier Sodium Polyacrylates and 35 weight portion nonionic emulsifier polypropylene glycols.
The consumption of above-mentioned all substances is in parts by weight.
Take by weighing raw material by following proportioning and produce the black floor tile:
24 kilograms of method for preparing microencapsulated phase change material powders, 182 unsaturated polyester resins 7 kilograms of (Shenyang Ward chemistry Co., Ltd), 335 saturated resins 0.6 kilogram of (Shenyang Ward chemistry Co., Ltd), 30 kilograms of quartz sands, 15 kilograms in aluminium oxide, calcium carbonate powder double centner, 0.5 kilogram of sodium metasilicate, 0.015 kilogram of cobalt iso-octoate, 0.15 kilogram of methyl ethyl ketone peroxide, 0.15 kilogram of iron oxide black.Above-mentioned powder material is placed in the refiner, add 25 kilograms in water, the mixing and stirring form slurry; Be positioned in the A/ZKX-2 vacuum forming machine mould slurry fixed-type; The blank that above-mentioned make-up machine makes is heated to 65 ℃, treat to carry out the demoulding, maintenance after the blank cooled and solidified, obtain the square stock that specification is 0.6m * 0.6m * 2.5m; With gang saw square stock is cut into the hair plates that thickness is 15mm, dry; Repair plate face pore with 182 unsaturated polyester resins (Shenyang Ward chemistry Co., Ltd) strike-through, handle promptly getting the black floor tile that thickness is 12mm through fine-grinding and polishing.Every performance indications of product and see table 2 for details with black glaze floor tile contrast that Guangdong Province Yunfu Yueyun New Stone Material Co., Ltd. existing production technology is produced.
The energy-saving black floor tile of table 2 material containing micro-capsule phase change performance indications
Performance Test result Prior art
The wear-resisting rate/(g/cm of the compressive strength of the bending strength of the thermal discharge of quantity of heat storage/(J/g)/(J/g)/(MPa)/(MPa) 3) the linear heat of Mohs' hardness is swollen/(g/ ℃) ??151.4 ??138.3 ??20.3 ??120.5 ??3×10 -3??4 ??1～4×10 -5 ??68.5 ??60.1 ??20 ??121 ??2.8×10 -3??4 ??1～4×10 -5
By being compared with the prior art as can be known, its heat accumulation thermal discharge of novel stone material of the present invention's development all exceeds nearly 80J/g than prior art, thereby be enough to show that the novel stone material that the present invention develops has better heat accumulation and heat release function, and can be good at regulating indoor temperature, reach purpose of energy saving.Product actual measurement bending strength and wear-resisting rate slightly are better than prior art, and compressive strength, Mohs' hardness and linear expansion coefficient etc. are suitable with prior art.
Embodiment 3:
The preparation double shell microcapsule phase change material:
(1) emulsification of core: 4 parts of TDI are total to molten formation core solution with 58 parts of n-octadecanes under 65 ℃ condition; Core solution is added in 18 parts of the deionized waters being dissolved with 0.2% (weight) protecting colloid hydroxyethylcellulose and 1.6% (weight) emulsifying agent emulsification 15min under the condition of 8000rpm, formation core emulsion;
(2) hypostracum coats: drip 4 part of 45% (weight) ethylenediamine (EDA) aqueous solution in emulsion under 350rpm, 65 ℃ of conditions, after dropwising, reacted 1.5 hours, obtain the microcapsule emulsion of polyureas parcel;
(3) preparation of outer shell prepolymer: get and contain 16 parts of the deionized waters that 7% (weight) melamine and 15% (weight) concentration are the formalin of 35% (weight), it with mass concentration 90% triethanolamine adjust pH to 8, be warming up to 70 ℃, stir, to the transparent carbamide performed polymer that gets of solution;
(4) outer shell coats: the melamine formaldehyde resin performed polymer is added in the microcapsule emulsion of step (2) preparation, it with mass concentration 10% citric acid solution adjust pH to 5.5, under 70 ℃ of conditions, reaction is 2 hours under the condition of 300rpm, cooling, discharging promptly gets microcapsule solution, more after filtration, wash, be drying to obtain the microcapsules powder.
Described emulsifying agent is the compound emulsifying agent that contains 70 weight portion anion emulsifier Sodium Polyacrylates and 30 weight portion nonionic emulsifier polypropylene glycols.
The consumption of above-mentioned all substances is in parts by weight.
Take by weighing raw material by following proportioning and produce green floor tile:
32 kilograms of method for preparing microencapsulated phase change material powders, 182 unsaturated polyester resins 10 kilograms of (Shenyang Ward chemistry Co., Ltd), 335 saturated resins 0.8 kilogram of (Shenyang Ward chemistry Co., Ltd), 30 kilograms of quartz sands, 20 kilograms in aluminium oxide, 130 kilograms of marble particles, 0.8 kilogram of RTV organosilicon (Dongguan City Ruo Lin trade Co., Ltd), 0.02 kilogram of cobalt iso-octoate, 0.2 kilogram of methyl ethyl ketone peroxide, 0.2 kilogram of chrome green.Above-mentioned powder material is placed in the refiner, add 32 kilograms in water, the mixing and stirring form slurry; Be positioned in the A/ZKX-1 vacuum forming machine mould slurry fixed-type; The blank that above-mentioned make-up machine makes is heated to 60 ℃, treat to carry out the demoulding, maintenance after the blank cooled and solidified, obtain the square stock that specification is 0.7m * 0.7m * 2.5m; With gang saw square stock is cut into the hair plates that thickness is 15mm, dry; Repair plate face pore with 182 unsaturated polyester resins (Shenyang Ward chemistry Co., Ltd) strike-through, handle promptly getting the green floor tile that thickness is 12mm through fine-grinding and polishing.The contrast of every performance indications of product and the emerald green floor tile produced with Guangdong Province Yunfu Yueyun New Stone Material Co., Ltd. existing production technology thereof sees table 3 for details.
The energy-saving green floor tile performance indications of table 3 material containing micro-capsule phase change
Performance Test result Prior art
The compressive strength of the bending strength of the thermal discharge of quantity of heat storage/(J/g)/(J/g)/(MPa)/(MPa) ??161.6 ??158.8 ??20.5 ??121 ??59.6 ??60.3 ??19.8 ??119.5
Wear-resisting rate/(g/cm 3) the linear heat of Mohs' hardness is swollen/(g/ ℃) ??3.05×10 -3??4 ??1～4×10 -5 ??3×10 -3??4 ??1～4×10 -5
By being compared with the prior art as can be known, its heat accumulation thermal discharge of novel stone material of the present invention's development all exceeds nearly 100J/g than prior art, thereby be enough to show that the novel stone material that the present invention develops has better heat accumulation and heat release function, and can be good at regulating indoor temperature, reach purpose of energy saving.Product actual measurement bending strength, compressive strength and wear-resisting rate slightly are better than prior art, and Mohs' hardness and linear expansion coefficient etc. are suitable with prior art.
Embodiment 4:
The preparation double shell microcapsule phase change material:
(1) emulsification of core: count by weight, 3 parts of TDI are total to molten formation core solution with 65 parts of paraffin under 70 ℃ condition; Core solution is added in 20 parts of the deionized waters being dissolved with 0.2% (weight) protecting colloid hydroxyethylcellulose and 1.8% (weight) emulsifying agent emulsification 15min under the condition of 9000rpm, formation core emulsion;
(2) hypostracum coats: drip 3 part of 65% (weight) ethylenediamine (EDA) aqueous solution in emulsion under 350rpm, 70 ℃ of conditions, after dropwising, reacted 1.5 hours, obtain the microcapsule emulsion of polyureas parcel;
(3) preparation of outer shell prepolymer: get and contain in 12 parts of the deionized waters of formalin that 7% (weight) melamine and 15% (weight) concentration are 40% (weight), it with mass concentration 90% triethanolamine adjust pH to 7.5, be warming up to 70 ℃, stir, to the transparent carbamide performed polymer that gets of solution;
(4) outer shell coats: the melamine formaldehyde resin performed polymer is added in the microcapsule emulsion of step (2) preparation, it with mass concentration 10% citric acid solution adjust pH to 5.5, under 70 ℃ of conditions, reaction is 2 hours under the condition of 300rpm, cooling, discharging promptly gets microcapsule solution, more after filtration, wash, be drying to obtain the microcapsules powder.
Described emulsifying agent is the compound emulsifying agent that contains 50 weight portion anion emulsifier Sodium Polyacrylates and 50 weight portion nonionic emulsifier polypropylene glycols.The consumption of above-mentioned all substances is in parts by weight.
Take by weighing raw material by following proportioning and produce yellow walltile:
45 kilograms of the made microencapsulated phase change material powders of said method, 182 unsaturated polyester resins 6 kilograms of (Shenyang Ward chemistry Co., Ltd), 335 saturated resins 0.5 kilogram of (Shenyang Ward chemistry Co., Ltd), 30 kilograms of silica flours, 85 kilograms of calcium carbonate powders, RTV organosilicon 0.15 kilogram of (Dongguan City Ruo Lin trade Co., Ltd), 0.01 kilogram of cobalt iso-octoate, 0.1 kilogram of methyl ethyl ketone peroxide, 0.1 kilogram of iron oxide yellow.Above-mentioned powder material is placed in the refiner, add 20 kilograms in water, the mixing and stirring form slurry; Be positioned in the A/ZKX-3 vacuum forming machine mould slurry fixed-type; The blank that above-mentioned make-up machine makes is heated to 55 ℃, treat to carry out the demoulding, maintenance after the blank cooled and solidified, obtain the square stock that specification is 0.3m * 0.4m * 2.5m; With gang saw square stock is cut into the hair plates that thickness is 12mm, dry; Repair plate face pore with 182 unsaturated polyester resins (Shenyang Ward chemistry Co., Ltd) strike-through, handle promptly getting the yellow walltile that thickness is 10mm through fine-grinding and polishing.The contrast of every performance indications of product and the ecru walltile produced with Guangdong Province Yunfu Yueyun New Stone Material Co., Ltd. existing production technology thereof sees table 4 for details.
The energy-saving yellow walltile performance indications of table 4 material containing micro-capsule phase change
Performance Test result Prior art
The wear-resisting rate/(g/cm of the compressive strength of the bending strength of the thermal discharge of quantity of heat storage/(J/g)/(J/g)/(MPa)/(MPa) 3) the linear heat of Mohs' hardness is swollen/(g/ ℃) ??173.1 ??171.2 ??18 ??115 ??2.88×10 -3??3 ??2～4×10 -5 ??60.4 ??59.3 ??18 ??110 ??2.85×10 -3??3 ??2～4×10 -5
By being compared with the prior art as can be known, its heat accumulation thermal discharge of novel stone material of the present invention's development all exceeds nearly 110J/g than prior art, thereby be enough to show that the novel stone material that the present invention develops has better heat accumulation and heat release function, and can be good at regulating indoor temperature, reach purpose of energy saving.Product actual measurement compressive strength and wear-resisting rate slightly are better than prior art, and bending strength, Mohs' hardness and linear expansion coefficient etc. are suitable with prior art.
Embodiment 5:
The preparation double shell microcapsule phase change material:
(1) emulsification of core: count by weight, 3.5 parts of TDI are total to molten formation core solution with 65 parts of paraffin under 65 ℃ condition; Core solution is added in 15 parts of the deionized waters being dissolved with 0.2% (weight) protecting colloid hydroxyethylcellulose and 1.8% (weight) emulsifying agent emulsification 15min under the condition of 9000rpm, formation core emulsion;
(2) hypostracum coats: drip 2.5 part of 45% (weight) ethylenediamine (EDA) aqueous solution in emulsion under 350rpm, 65 ℃ of conditions, after dropwising, reacted 1.5 hours, obtain the microcapsule emulsion of polyureas parcel; (3) preparation of outer shell prepolymer: get and contain in 14 parts of the deionized waters of formalin that 7% (weight) melamine and 15% (weight) concentration are 37% (weight), it with mass concentration 90% triethanolamine adjust pH to 7.5, be warming up to 65 ℃, stir, to the transparent carbamide performed polymer that gets of solution;
(4) outer shell coats: the melamine formaldehyde resin performed polymer is added in the microcapsule emulsion of step (2) preparation, it with mass concentration 10% citric acid solution adjust pH to 5.5, under 75 ℃ of conditions, reaction is 2 hours under the condition of 300rpm, cooling, discharging promptly gets microcapsule solution, more after filtration, wash, be drying to obtain the microcapsules powder.
Described emulsifying agent is the compound emulsifying agent that contains 55 weight portion anion emulsifier Sodium Polyacrylates and 45 weight portion nonionic emulsifier polypropylene glycols.The consumption of above-mentioned all substances is in parts by weight.
Take by weighing raw material by following proportioning and produce the commentaries on classics of black metope:
80 kilograms of the made microencapsulated phase change material powders of said method, 182 unsaturated polyester resins 7 kilograms of (Shenyang Ward chemistry Co., Ltd), 335 saturated resins 0.6 kilogram of (Shenyang Ward chemistry Co., Ltd), 30 kilograms of quartz sands, 15 kilograms in aluminium oxide, 110 kilograms of marble particles, 0.5 kilogram of sodium metasilicate, 0.015 kilogram of cobalt iso-octoate, 0.15 kilogram of methyl ethyl ketone peroxide, 0.15 kilogram of carbon black.Above-mentioned powder material is placed in the refiner, add 25 kilograms in water, the mixing and stirring form slurry; Be positioned in the A/ZKX-3 vacuum forming machine mould slurry fixed-type; The blank that above-mentioned make-up machine makes is heated to 55 ℃, treat to carry out the demoulding, maintenance after the blank cooled and solidified, obtain the square stock that specification is 0.3m * 0.4m * 2.5m; With gang saw square stock is cut into the hair plates that thickness is 12mm, dry; Repair plate face pore with 182 unsaturated polyester resins (Shenyang Ward chemistry Co., Ltd) strike-through, handle promptly getting the yellow walltile that thickness is 10mm through fine-grinding and polishing.The contrast of every performance indications of product and the black walltile produced with Guangdong Province Yunfu Yueyun New Stone Material Co., Ltd. existing production technology thereof sees table 5 for details.
The energy-saving black walltile of table 5 material containing micro-capsule phase change performance indications
Performance Test result Prior art
The wear-resisting rate/(g/cm of the compressive strength of the bending strength of the thermal discharge of quantity of heat storage/(J/g)/(J/g)/(MPa)/(MPa) 3) the linear heat of Mohs' hardness is swollen/(g/ ℃) ??178.6 ??176.8 ??19.1 ??118.3 ??2.88×10 -3??3 ??2～4×10 -5 ??59.4 ??57.6 ??19.5 ??119 ??2.85×10 -3??3 ??2～4×10 -5
By being compared with the prior art as can be known, its heat accumulation thermal discharge of novel stone material of the present invention's development all exceeds nearly 120J/g than prior art, thereby be enough to show that the novel stone material that the present invention develops has better heat accumulation and heat release function, and can be good at regulating indoor temperature, reach purpose of energy saving.Product is surveyed wear-resisting rate and slightly is better than prior art, and bending strength, Mohs' hardness, compressive strength and linear expansion coefficient etc. are suitable with prior art.
Embodiment 6:
Take by weighing raw material by following proportioning and produce red green decorative pattern walltile:
25 kilograms of commercially available PCM208 paraffin system microencapsulated phase change materials (producing), 182 unsaturated polyester resins 10 kilograms of (Shenyang Ward chemistry Co., Ltd), 335 saturated resins 0.8 kilogram of (Shenyang Ward chemistry Co., Ltd), 30 kilograms of quartz sands, 20 kilograms in aluminium oxide, 135 kilograms of calcium carbonate powders, RTV organosilicon 0.8 kilogram of (Dongguan City Ruo Lin trade Co., Ltd), 0.02 kilogram of cobalt iso-octoate, 0.2 kilogram of methyl ethyl ketone peroxide by Chongqing Hautwell Science ﹠ Technology Co., Ltd..Two parts of configuration said mixtures add 0.2 kilogram of iron oxide red respectively, 0.2 kilogram of chrome green; Above-mentioned powder material is placed refiner respectively, and each adds 32 kg water, stirs into slurry; By texture trend, the color and luster requirement of product, in A/ZKX-3 vacuum forming machine mould, be docile and obedient the preface cloth, reach the design requirement of product; The above-mentioned blank that makes is heated to 65 ℃, treat to carry out the demoulding, maintenance after the blank cooled and solidified, obtain the square stock that specification is 0.3m * 0.4m * 2.5m; With gang saw square stock is cut into the hair plates that thickness is 12mm, dry; Repair plate face pore with 182 unsaturated polyester resins (Shenyang Ward chemistry Co., Ltd) strike-through, handle promptly getting the yellowish green decorative pattern walltile that thickness is 10mm through fine-grinding and polishing.The contrast of the yellowish green colour mixture walltile that the existing production technology of the every performance indications of product and Guangdong Province Yunfu Yueyun New Stone Material Co., Ltd. is produced sees table 6 for details.
The energy-saving artificial marble performance indications of table 6 material containing micro-capsule phase change
Performance Test result Prior art
The wear-resisting rate/(g/cm of the compressive strength of the bending strength of the thermal discharge of quantity of heat storage/(J/g)/(J/g)/(MPa)/(MPa) 3) the linear heat of Mohs' hardness is swollen/(g/ ℃) ??152.1 ??143.8 ??20 ??116.1 ??2.8×10 -3??3 ??2～4×10 -5 ??65.2 ??61.4 ??19.2 ??117 ??2.85×10 -3??3 ??2～4×10 -5
By being compared with the prior art as can be known, its heat accumulation thermal discharge of Novel stone of the present invention's development all exceeds nearly 80 J/g than prior art, thereby be enough to show that the Novel stone that the present invention develops has better heat accumulation and heat release function, and can be good at regulating indoor temperature, reach energy-conservation purpose. Product actual measurement bending strength slightly is better than prior art, compressive strength, wear-resisting rate, Mohs' hardness and suitable with prior art with linear expansion coefficient etc.

Claims (5)

1, a kind of preparation method of energy-saving artificial marble of material containing micro-capsule phase change is characterized in that comprising the steps:
(1) with microcapsules powder, unsaturated polyester resin Binder Materials and silica flour according to 0.6～3: 0.2～0.5: 1 part by weight mixes;
(2) in 1: 10 ratio step (1) gained mixture is added in the artificial stone base material, and add pigment, curing agent methyl ethyl ketone peroxide and promoter cobalt iso-octoate, form the stone material base-material; By the weight percent meter that accounts for the stone material base-material, pigment accounts for 0.05～0.15%, and the curing agent methyl ethyl ketone peroxide accounts for 0.05～0.2%, and the promoter cobalt iso-octoate accounts for 0.01～0.05%;
(3) step (2) gained stone material base-material is put into the vacuum forming machine mould and after the vibration moulding, got finished product;
Microencapsulated phase change material is 10%～35% at weight content in the described finished product, and described microencapsulated phase change material powder is meant that microcapsules kernel phase transition temperature is-50～150 ℃ micron or a nano-powder material.
2, the preparation method of the energy-saving artificial marble of material containing micro-capsule phase change according to claim 1 is characterized in that: described microcapsules powder prepares by the following method:
(1) emulsification of core: count by weight, 1.5～5.4 parts of TDI are total to molten formation core solution with 55～85 parts of n-octadecanes or paraffin under 60～70 ℃ condition; It is that 0.1%～0.3% protecting colloid hydroxyethylcellulose and weight content are in the deionized water of 1.2%～1.8% emulsifying agent that the adding of core solution is dissolved with weight content, and emulsification 10～20min under the condition of 5000～9000rpm forms the core emulsion;
(2) hypostracum coats: drip 2.1～4.8 part of 45%～65% (weight) ethylenediamine solution in the core emulsion that makes under 300～400rpm, 60～70 ℃ of conditions, after dropwising, reacted 1～2 hour, obtain the microcapsule emulsion of polyureas parcel;
(3) preparation of outer shell prepolymer: with 6.0～10.8 parts of melamines and 10.8～24.6 parts of weight percent concentration is that 35～40% formalins join in 10～20 parts of deionized waters, with mass concentration 90% triethanolamine adjust pH to 7～8, be warming up to 70～75 ℃, stir, to the transparent carbamide performed polymer that gets of solution;
(4) outer shell coats: the melamine formaldehyde resin performed polymer is added in the microcapsule emulsion of step (2) preparation, with mass concentration 10% citric acid solution adjust pH to 5～6, under 70～75 ℃ of conditions, under the condition of 300～400rpm, reacted 1～2 hour, cooling, discharging promptly gets microcapsule solution, more after filtration, wash, be drying to obtain the microcapsules powder.
3,, it is characterized in that described artificial stone base material is one or more in quartz sand, aluminium oxide, calcium carbonate powder and the marble particle according to the energy-saving method for imitation marble of the described material containing micro-capsule phase change of claim 2.
4, the preparation method of the energy-saving artificial marble of material containing micro-capsule phase change according to claim 2 is characterized in that: the weight percent concentration of formalin is 37%.
5, according to the energy-saving method for imitation marble of the described material containing micro-capsule phase change of claim 2, it is characterized in that: described emulsifying agent is that weight ratio is the compound emulsifying agent that 1: 1～2.3 anion emulsifier Sodium Polyacrylate and nonionic emulsifier polypropylene glycol are formed.
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CN101805151A (en) * 2010-03-26 2010-08-18 广州戈兰迪高分子材料有限公司 Noctilucent artificial stone and preparation method thereof
CN104003652A (en) * 2014-05-16 2014-08-27 中科院广州化学有限公司 Phase-transition insulation artificial stone sheet material containing stone material waste residue, preparation method and application thereof
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CN101805151A (en) * 2010-03-26 2010-08-18 广州戈兰迪高分子材料有限公司 Noctilucent artificial stone and preparation method thereof
CN104003652A (en) * 2014-05-16 2014-08-27 中科院广州化学有限公司 Phase-transition insulation artificial stone sheet material containing stone material waste residue, preparation method and application thereof
CN104003652B (en) * 2014-05-16 2015-09-23 中科院广州化学有限公司 A kind of insulation of the inversion of phases containing stone material waste residue artificial slabstone and preparation method thereof and application
CN104745050A (en) * 2015-03-31 2015-07-01 艾金富 Corrosion resistant steel coating
US10597945B2 (en) * 2016-02-12 2020-03-24 Dover Chemical Corporation Coiled-tubing fluid-lubricant composition and related methods
CN107672085A (en) * 2016-08-01 2018-02-09 波音公司 Force-responsive pre-preg complex method, system and device
CN107572891A (en) * 2017-08-29 2018-01-12 无为县鑫品石业有限公司 One kind synthesis toughness marble and its manufacture method
CN109096738A (en) * 2018-07-12 2018-12-28 宁波蒙曼生物科技有限公司 A kind of novel tree epoxy-type artificial stone and preparation method thereof
CN109096738B (en) * 2018-07-12 2021-03-16 福建鹏翔实业有限公司 Resin type artificial stone and preparation method thereof

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