CN102617105B - Polyvinyl chloride resin reinforced geopolymer composite material and preparation method thereof - Google Patents
Polyvinyl chloride resin reinforced geopolymer composite material and preparation method thereof Download PDFInfo
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- CN102617105B CN102617105B CN201210081093.6A CN201210081093A CN102617105B CN 102617105 B CN102617105 B CN 102617105B CN 201210081093 A CN201210081093 A CN 201210081093A CN 102617105 B CN102617105 B CN 102617105B
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Abstract
The invention discloses a polyvinyl chloride resin reinforced geopolymer composite material and a preparation method thereof. The preparation method comprises the following steps of: mixing metakaolin, water glass solution and water uniformly at room temperature to obtain an alkali-activated geopolymer; and uniformly mixing 50-70wt% of alkali-activated geopolymer, 29.13--45.45wt% of polyvinyl chloride resin and 0.87-4.55% of heat stabilizer by using a high-speed mixer, plastifying, performing compaction molding and demolding to finally obtain the polyvinyl chloride resin reinforced geopolymer composite material. The prepared polyvinyl chloride resin reinforced geopolymer composite material has good breaking strength higher than that of the geopolymer, has early strength, high strength, high toughness and good strength stability, wherein the maximum breaking strength is higher than 78.5Mpa. according to the invention, the key technical problems of the geopolymer made of metakaolin, such as high fragility and poor toughness, are solved.
Description
Technical field:
The invention belongs to the preparation of inorganic-organic composite material class, be specifically related to a kind of polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material and preparation method thereof.
Background technology:
Geopolymer is that a class is with inorganic [SiO
4]
4-, [AlO
4]
5-tetrahedron is main skeleton, the inorganic silicon-aluminum hydrochlorate being formed by ionic linkage, covalent bonding, and its structure is irregular tridimensional network, alkali metal cation and alkaline earth metal cation filling network space and the non-crystalline state that forms are to the solid material of semi-crystalline state.The excellent properties such as it has that ultimate compression strength is high, environmental protection, high temperature resistant, corrosion-resistant, volumetric shrinkage is little and thermal conductivity is low, but its tension, bending strength are low, and ultimate strain is little, shock strength is poor, and fragility is large, easy to crack, exist serious endurance issues, limited its range of application.For above-mentioned shortcoming, conventionally need to add mechanics and physicals that some organism or inorganics increase geopolymer.At present, the people's such as Zhang Yaojun patent of invention (application number 200910022109.4,200910022112.6,200910022803.6,201010153097.1) has been reported the preparation method of organic polymer and geopolymer composite gelled material.In these four patents, organic polymer refers to respectively the organic polymer vinyl acetate latex powder of styrene/acrylic methyl esters copolymer emulsion, styrene/acrylic butyl ester copolymer emulsion, binary built and polyacrylate resin emulsion, butyl acrylate-Emulsion acrylic resin, although be improved by adding matrix material folding strength prepared by above organic polymer, but the amplitude that intensity improves is not very good, the folding strength in its 28d length of time is 9.0Mpa to the maximum, than inorganic silicon-aluminum silicate polymer, has improved 2.08 times.In addition, take geopolymer as matrix, in preparation process, add toughness and splitting resistance that various fibers improve geopolymer, although adding of fiber can significantly strengthen its intensity, have the shortcomings such as expensive, complex forming technology.
Summary of the invention:
For existing alkali, excite geopolymer gelling material ubiquity fragility large, the defect of poor toughness, the object of the invention is to, adopt alkali shooting techniques, organic polymer resin enhancement techniques, the approach that pressurized forming technique combines provides a kind of morning strong, high-strength, high-ductility, strength property is stable, alternative stupalith, organic and timber etc. makes sheet material, tubing, bar, insulating material, cryogenic material etc., there is waterproof, erosion resistance, weather resistance, weathering resistance, fire performance, the polyvinyl chloride (PVC) RESINS of the advantages such as splitting resistance is good strengthens geopolymer matrix material and preparation method thereof.
The preparation method of the geopolymer matrix material that polyvinyl chloride (PVC) RESINS strengthens realizes by following steps: by metakaolin, water glass solution and water, by basal component, be,
After at room temperature stirring, make alkali and excite geopolymer; By 50-70%(mass percent, rear with) alkali excite the polyvinyl chloride (PVC) RESINS of geopolymer, 29.13-45.45% and the thermo-stabilizer of 0.87-4.55% to mix, plasticate, be subject to molded, the demoulding to obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material through high-speed mixer.
Described metakaolin be by kaolin, under the condition of 500-800 ℃, calcine 1.5-2.5h, grinding becomes 100-1000 order fine powder, its main ingredient mass percent content is respectively Al
2o
342-46%, SiO
250-57%, other 1%-4%.
The aqueous solution that the water glass that described water glass solution is 1.5-3.2 by modulus and NaOH are mixed with, 12-48h is standby in sealing ageing.
Described thermo-stabilizer comprises one or more the mixture in Ca-Zn composite heat stabilizer, barium stearate, Zinic stearas, rare earth composite stabilizer, methyl organotin, epoxy soybean oil.
Described its temperature of plasticating is 140-180 ℃, and the time is 4-8min.
Described to be subject to molded its pressure be 5-15Mpa, and temperature is 160-180 ℃, and the time is 5-10min.
Polyvinyl chloride (PVC) RESINS of the present invention strengthens geopolymer matrix material and preparation method thereof, the technique effect bringing is: adopt organic polymer polyvinyl chloride (PVC) RESINS to carry out geopolymer structurally-modified, organic polymer and inorganic polymer are mixed equably.Polyvinyl chloride (PVC) RESINS polyvinyl chloride molecular chain after over-mastication forms the interspersed three-dimensional net structure of new inorganic-organic with the Si-O-Al network of geopolymer, improve the microtexture of geopolymer, and the add-on of polyvinyl chloride (PVC) RESINS is larger, thereby significantly improved the toughness of matrix material, this matrix material folding strength is all higher than geopolymer, more than high breaking strength reaches 78.5Mpa; Solved geopolymer prepared by metakaolin and had that fragility is large, the key technical problem of poor toughness.In addition, product polyvinyl chloride (PVC) RESINS of the present invention strengthens the good characteristic that geopolymer matrix material not only has geopolymer, the characteristic also with polyvinyl chloride (PVC) RESINS, alternative stupalith, organic and timber etc. are made sheet material, tubing, bar, insulating material, cryogenic material etc.Meanwhile, its preparation technology is simple, have good processibility, without maintenance, with short production cycle, and constant product quality has the utility value of industry.
The present invention has above-mentioned plurality of advantages and practical value, no matter it all has larger improvement in preparation and application method, product efficacy, has technically significant progress, and has produced handy and practical effect.
Novelty part of the present invention is: (1) has proposed innovatively organic polymer polyvinyl chloride (PVC) RESINS and geopolymer carried out to the novel method of toughening modifying.(2) propose innovatively the approach that alkali shooting techniques, organic polymer resin enhancement techniques, pressurized forming technique combine and geopolymer is carried out to the novel method of toughening modifying, make matrix material there is good mechanical property.
Embodiment:
Be below inventive embodiment, it should be noted that, these embodiment only annotate the present invention better for contriver, the invention is not restricted to these embodiment.
Embodiment 1: take in the water glass that 22.28g sodium hydroxide is dissolved in 130.36g3.1 modulus sealing ageing 24h; Take metakaolin 130g, water 9.20g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; (model is SG to take polyvinyl chloride (PVC) RESINS
5) 277.94g, Ca-Zn composite heat stabilizer 13.90g, excites geopolymer in high-speed mixer, to mix after 2min with load weighted polyvinyl chloride (PVC) RESINS and calcium-zinc composite stabilizing agent in the alkali of preparation, is placed in two roller mills and plasticates, 172 ℃ of plasticating temperatures, time 5min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 176 ℃ of mold temperatures, molding time 5min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 78.5Mpa.
Embodiment 2: take in the water glass that 30.85g sodium hydroxide is dissolved in 180.50g3.1 modulus sealing ageing 24h; Take metakaolin 180g, water 12.74g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; (model is SG to take polyvinyl chloride (PVC) RESINS
5) 254.14g, Ca-Zn composite heat stabilizer 15.25g, excites geopolymer in high-speed mixer, to mix after 2min with load weighted polyvinyl chloride (PVC) RESINS and calcium-zinc composite stabilizing agent in the alkali of preparation, is placed in two roller mills and plasticates, 176 ℃ of plasticating temperatures, time 4min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 176 ℃ of mold temperatures, molding time 5min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 69.26Mpa.
Embodiment 3: take in the water glass that 32.57g sodium hydroxide is dissolved in 190.53g3.1 modulus sealing ageing 12h; Take metakaolin 190g, water 20.73g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; (model is SG to take polyvinyl chloride (PVC) RESINS
5) 220.38g, Ca-Zn composite heat stabilizer 13.22g, excites geopolymer in high-speed mixer, to mix after 1min with load weighted polyvinyl chloride (PVC) RESINS and calcium-zinc composite stabilizing agent in the alkali of preparation, is placed in two roller mills and plasticates, 175 ℃ of plasticating temperatures, time 5.5min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 173 ℃ of mold temperatures, molding time 6min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 68.35Mpa.
Embodiment 4: take in the water glass that 37.71g sodium hydroxide is dissolved in 220.62g3.1 modulus sealing ageing 24h; Take metakaolin 220g, water 15.57g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; (model is SG to take polyvinyl chloride (PVC) RESINS
5) 199.69g, Ca-Zn composite heat stabilizer 11.98g, excites geopolymer in high-speed mixer, to mix after 1min with load weighted polyvinyl chloride (PVC) RESINS and calcium-zinc composite stabilizing agent in the alkali of preparation, is placed in two roller mills and plasticates, 170 ℃ of plasticating temperatures, time 6min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 175 ℃ of mold temperatures, molding time 5min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 58.20Mpa.
Embodiment 5: take in the water glass that 22.28g sodium hydroxide is dissolved in 130.36g3.1 modulus sealing ageing 24h; Take metakaolin 130g, water 9.20g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; Take pvc resin paste grade (model is P-440) 277.94g, Ca-Zn composite heat stabilizer 13.90g, excite geopolymer in high-speed mixer, to mix after 2min with load weighted pvc resin paste grade and calcium-zinc composite stabilizing agent in the alkali of preparation, be placed in two roller mills and plasticate, 142 ℃ of plasticating temperatures, time 8min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 178 ℃ of mold temperatures, molding time 5min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 76.6Mpa.
Embodiment 6: take in the water glass that 30.85g sodium hydroxide is dissolved in 180.50g3.1 modulus sealing ageing 24h; Take metakaolin 180g, water 12.74g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; Take pvc resin paste grade (model is P-440) 254.14g, Ca-Zn composite heat stabilizer 15.25g, excite geopolymer in high-speed mixer, to mix after 1min with load weighted pvc resin paste grade and calcium-zinc composite stabilizing agent in the alkali of preparation, be placed in two roller mills and plasticate, 162 ℃ of plasticating temperatures, time 4.5min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 178 ℃ of mold temperatures, molding time 5min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 65.98Mpa.
Embodiment 7: take in the water glass that 32.57g sodium hydroxide is dissolved in 190.53g3.1 modulus sealing ageing 12h; Take metakaolin 190g, water 20.73g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; Take pvc resin paste grade (model is P-440) 212.36g, Ca-Zn composite heat stabilizer 21.24g, excite geopolymer in high-speed mixer, to mix after 1min with load weighted pvc resin paste grade and calcium-zinc composite stabilizing agent in the alkali of preparation, be placed in two roller mills and plasticate, 175 ℃ of plasticating temperatures, time 5.5min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 175 ℃ of mold temperatures, molding time 6min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 64.14Mpa.
Embodiment 8: take in the water glass that 37.71g sodium hydroxide is dissolved in 220.62g3.1 modulus sealing ageing 24h; Take metakaolin 220g, water 15.58g, at room temperature by the water glass solution of metakaolin, ageing and water, inserts and two turn double speed and only starch in stirrer and stir, and stirs and forms the slurry mixing, and makes alkali and excites geopolymer; Take pvc resin paste grade (model is P-440) 192.43g, Ca-Zn composite heat stabilizer 19.24g, excite geopolymer in high-speed mixer, to mix after 1min with load weighted pvc resin paste grade and calcium-zinc composite stabilizing agent in the alkali of preparation, be placed in two roller mills and plasticate, 155 ℃ of plasticating temperatures, time 6min plasticates; The thin slice of plasticating is placed in to steel die, on hydropress, be subject to molded, forming pressure 15Mpa, 175 ℃ of mold temperatures, molding time 5min; Be cooled to 40 ℃ of demouldings, obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material.
Measuring the folding strength that polyvinyl chloride (PVC) RESINS prepared by this embodiment strengthens geopolymer matrix material is 60.20Mpa.
Claims (6)
1. a preparation method for the geopolymer matrix material that polyvinyl chloride (PVC) RESINS strengthens, realizes by following steps: by metakaolin, water glass solution and water, by basal component, be,
after at room temperature stirring, make alkali and excite geopolymer; By 50-70%(mass percent, rear with) alkali excite the polyvinyl chloride (PVC) RESINS of geopolymer, 29.13-45.45% and the thermo-stabilizer of 0.87-4.55% to mix, plasticate, be subject to molded, the demoulding to obtain polyvinyl chloride (PVC) RESINS and strengthen geopolymer matrix material through high-speed mixer.
2. the preparation method of the geopolymer matrix material that a kind of polyvinyl chloride (PVC) RESINS according to claim 1 strengthens, it is characterized in that, described metakaolin be by kaolin, under the condition of 500-800 ℃, calcine 1.5-2.5h, grinding becomes 100-1000 order fine powder, its main ingredient mass percent content is respectively Al
2o
342-46%, SiO
250-57%, other 1%-4%.
3. the preparation method of the geopolymer matrix material that a kind of polyvinyl chloride (PVC) RESINS according to claim 1 strengthens, it is characterized in that, the aqueous solution that the water glass that described water glass solution is 1.5-3.2 by modulus and NaOH are mixed with, 12-48h is standby in sealing ageing.
4. the preparation method of the geopolymer matrix material that a kind of polyvinyl chloride (PVC) RESINS according to claim 1 strengthens, it is characterized in that, described thermo-stabilizer comprises one or more the mixture in Ca-Zn composite heat stabilizer, barium stearate, Zinic stearas, rare earth composite stabilizer, methyl organotin, epoxy soybean oil.
5. the preparation method of the geopolymer matrix material that a kind of polyvinyl chloride (PVC) RESINS according to claim 1 strengthens, is characterized in that, described in its temperature of plasticating be 140-180 ℃, the time is 4-8min.
6. the preparation method of the geopolymer matrix material that a kind of polyvinyl chloride (PVC) RESINS according to claim 1 strengthens, is characterized in that, described in to be subject to molded its pressure be 5-15MPa, temperature is 160-180 ℃, the time is 5-10min.
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| CN103232182B (en) * | 2013-04-24 | 2014-12-03 | 广西交通科学研究院 | Geopolymer/emulsified asphalt composite material and preparation method thereof |
| CN106086401B (en) * | 2016-06-23 | 2018-01-02 | 北京科技大学 | A kind of method being applied to inorganic polymer in iron mineral powder agglomeration technique |
| CN110066139A (en) * | 2019-05-28 | 2019-07-30 | 四川益好优科环保科技有限公司 | A kind of the radiation polycondensation melamine resin material and preparation method of high solid waste filling |
| CN111995354B (en) * | 2020-08-31 | 2021-10-22 | 武汉大学 | Reinforced fly ash-based polymer and preparation method thereof |
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| CN101302318A (en) * | 2008-07-07 | 2008-11-12 | 四川大学 | Polychloroethylene / organic modified sheet silicate nano-composite material |
| CN101891443A (en) * | 2010-06-28 | 2010-11-24 | 巢启 | Heat-insulating profile with low heat conductivity |
| CN102219460A (en) * | 2011-03-16 | 2011-10-19 | 广西大学 | Organic and inorganic composite insulation material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302318A (en) * | 2008-07-07 | 2008-11-12 | 四川大学 | Polychloroethylene / organic modified sheet silicate nano-composite material |
| CN101891443A (en) * | 2010-06-28 | 2010-11-24 | 巢启 | Heat-insulating profile with low heat conductivity |
| CN102219460A (en) * | 2011-03-16 | 2011-10-19 | 广西大学 | Organic and inorganic composite insulation material |
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