CN103059749A - Preparation method of modified silicate inorganic adhesive - Google Patents
Preparation method of modified silicate inorganic adhesive Download PDFInfo
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- CN103059749A CN103059749A CN2013100406364A CN201310040636A CN103059749A CN 103059749 A CN103059749 A CN 103059749A CN 2013100406364 A CN2013100406364 A CN 2013100406364A CN 201310040636 A CN201310040636 A CN 201310040636A CN 103059749 A CN103059749 A CN 103059749A
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Abstract
The invention relates to a preparation method of a modified silicate inorganic adhesive, which comprises the following steps: 1) grinding quartz sand and silicon carbide into powder; 2) preparing a cellulose acetate solution; 3) preparing a polyurethane prepolymer; 4) preparing a cellulose acetate emulsion; and 5) adding the cellulose acetate emulsion prepared in the step 4) into a 35-55 wt% potassium silicate water solution, stirring to react, adding right amounts of barium chloride, calcium stearate, quartz sand powder and silicon carbide powder, sufficiently stirring, and reacting for 40-55 minutes. The preparation technique is simple; and the prepared water-resistant inorganic adhesive has the advantages of favorable flexibility, water resistance and high adhesive force.
Description
Technical field
The present invention relates to a kind of preparation method of modified Portland inorganic adhesive, relate in particular to the preparation method of the modified Portland inorganic adhesive that a kind of snappiness is good, water-fast, bonding force is strong.
Background technology
The 90's of 20th century China's adhesives industries has entered the new stage of a high speed development.21st century, tackiness agent output rose to 379.28 ten thousand tons from 22.7 ten thousand tons from 2004 to 2009, and average growth rate per annum expects 2015 more than 10%, i.e. " 12 " plan end, and China's tackiness agent output will break through 6,000,000 tons of high pointes.In recent years, along with the development of the industries such as China's refractory materials, military project, aviation, in the urgent need to large quantities of tackiness agent that can in hot environment, use.
Theoretical investigation through the summary of many decades knowhow and system, the letex polymerization production technology is full-fledged, in the high molecular polymer preparation field, since the solution polymerization production technology since its exist necessarily be difficult to the defective that overcomes with and environmental pollution larger, the solution polymerization related-art process is gradually had more superiority letex polymerization production technology and technique and is replaced.Along with people's protection of the environment meaning grows with each passing day, the backroom boys more and more pays close attention to extremely related application of letex polymerization production technology.In the many decades, emulsion polymerization technology is under countless outstanding backroom boys' promotion, and constantly development on the basis of traditional emulsion polymerization technology, is constantly brought forth new ideas.The polymer emulsion method is varied now, and many modes such as inverse emulsion polymerization, microsuspension and emulsion polycondensation polymerization are arranged.Under new technique means, prepare the novel type product emulsion, as: the emulsion particle of microemulsion, special appearance structure, emulsion-type interpenetrating polymer networks, functional high-polymer polymer microballoon etc.Letex polymerization applies to prepare high molecular polymer widely, is one of the most effective high molecular polymer production method.
Letex polymerization applies to prepare high molecular polymer widely, one of the most effective high molecular polymer production method. the letex polymerization production technology is born in 19th-century mid-early stage, letex polymerization in history, the document that can investigate the earliest is that general headquarters adopt emulsion polymerization to prepare the synthetic rubber technology in the Beyer Co., Ltd of Germany, although there are many defectives in its production technology, but it is very approaching with now letex polymerization production technology, and its production formula is also ripe.Now, there are every year in the world billions of tons of macromolecule polymer materials to adopt the emulsion polymerisation process preparation, in the synthetic rubber field that letex polymerization is used the earliest, adopt the rubber of emulsion polymerization technology production to account for the rubber ultimate production more than 65 percent.1820s, the letex polymerization production technology still is in the budding stage, in its extensive utilization in industrial production of 1830s.Now, emulsion polymerization technology has been the extremely important integral part of polymer subject.Many high molecular polymers all are to adopt emulsion polymerization way to be prepared, such as synthetic chloroprene rubber, flocculation agent, coating, synthetic resins, medical polymer polymer materials and other a lot of extraordinary macromolecule polymer materials of using.Theoretical investigation through the summary of many decades knowhow and system, the letex polymerization production technology is full-fledged, in the high molecular polymer preparation field, since the solution polymerization production technology since its exist necessarily be difficult to the defective that overcomes with and environmental pollution larger, the solution polymerization related-art process is gradually had more superiority letex polymerization production technology and technique and is replaced.Along with people's protection of the environment meaning grows with each passing day, the backroom boys more and more pays close attention to extremely related application of letex polymerization production technology.The letex polymerization polymerization process is as follows: in the polymerization system; free radical enters the monomer droplet initiated polymerization; under the emulsifying agent provide protection, form the emulsion particle that mutually isolates to each other; free radical carries out addition polymerization in the emulsion particle; prepare the method for high molecular polymer with this, in the polymerization reaction system usually with water as dispersion medium.The concept of letex polymerization is that in water miscible liquid emulsion particle independent of each other, the monomer free radical carries out the technology that addition polymerization prepares high molecular polymer.Through exploring for a long time, people have proposed again the oligopolymer mechanism of nucleation, and when emulsifier concentration was lower than micelle-forming concentration in the polymerization system, polymerization system can't form micella, and in not having the polymerization system of micella, polymerization still can be carried out.Therefore, classical letex polymerization theory thinks that when having micella in the emulsion polymerization systems, polymerization is carried out with micella mechanism, and when not having micella in the emulsion polymerization systems, polymerization is take the oligopolymer mechanism of nucleation as main.
Common silicate adhesive modification mode has following several:
Physically modified: be called physically modified by physical route modifications such as sound, electricity, magnetic.
Ultrasonically-modified: USSR (Union of Soviet Socialist Republics) Jelinek in 1980 and domestic Xie Zuxi in 1991 have carried out modification with ultrasonic wave to water glass respectively, and the method has improved cohesive strength, but treating processes can expend the plenty of time, and DeGrain.
Magnetization modification: Czech Cajkova in 1978 and domestic Wang Xing beautiful jade in 1990 have carried out modification with Magnetic Field on Water glass respectively, and the method has reduced the consumption of water glass, but needs repeatedly circular treatment, and the post-modification effect disappeared substantially in 24 hours.
Chemical modification: the method that changes chemical reaction velocity and product is called chemical modification.
Heat modification: heat modification is that the way by the rising solidification value promotes that tackiness agent at utmost reacts curing, studies show that, after the silicate adhesive natural curing 2 days, be heated to 110 ℃ and be incubated 1 hour with 10 ℃/minute speed, then naturally cool to room temperature, the over-all properties of gained tackiness agent is best.Too early, too fast, too high, long type of heating, can cause the moisture in the glue-line sharply to volatilize, stay pore, cause the glue-line bubbling, reduce cohesive strength.Xu Feng makes tackiness agent intensity rise to 24.78MPa from 15.9MPa by heating, and rate of increase is 55.85%, and modified effect is very obvious.
Acidified modified: acidified modified is by increasing acid generation and the polycondensation that promotes silicic acid of glue-line.The long Rong Caiyong of Guo smeared the mineral acid modification in 1991, and Li Zhiping in 2003 is by adding the mineral acid modification, and Wang Pan was by adding the organic acid salt modification in 2009.Smear in three kinds of methods than adding easier operation, because tackiness agent is a kind of colloid, belong to Unstable Systems, if directly add the acids modification, will be because of the rapid variation of pH value, cause structural adhesive layer to destroy, the glue-line of primary solidification is smeared mineral acid then can not destroy structural adhesive layer.Experimental result shows that acidified modified rear tackiness agent water tolerance obviously improves, and strength growth rate is 31.21%.
Preferred consolidation agent modification: solidifying agent is that silicate adhesive solidifies requisite integral part, comprises silicofluoride take Sodium Silicofluoride as representative, the condensation of aluminum phosphate oxide compound three major types as the phosphoric acid salt of representative and silicon-dioxide as representative.The result comparison shows that by experiment: phosphate firming agent does not have toxicity, be widely used in the packaging industry of the non-harmful products such as food, but cost is expensive, and raw material is rare; Oxide compound solidifying agent cost is lower, but solidification effect is not good; Sodium Silicofluoride solidifying agent cost is low, and solidification effect is good, is to use at present the most general solidifying agent, but can discharges a small amount of HF gas during high temperature.
Composite modified: composite modified is the over-all properties that improves tackiness agent by the mixing of two or more tackiness agent, comprises that silicate-silicate is compound, and silicate-phosphoric acid salt is compound, and silicate-organic gel is compound.Zhu Jun in 2006 utilizes polyoxyethylene and silicate adhesive composite modified, and Tetsu in 2008 utilizes polyvinyl alcohol and silicate adhesive composite modified.Although three kinds of complex methods all are improved to some extent to water tolerance and mechanical property, but phosphoric acid salt is different with performance with silicate composition structure, and compound relatively difficulty is in addition because the difference of linear expansivity, at high temperature easier destruction glue-line reduces intensity.Equally, the compound also difficulty relatively of organic gel and silicate, the in addition adding of organic substance can reduce the hot strength of silicate adhesive greatly.At present, potassium silicate-water glass is compound more suitable, compound difficulty can not occur or reduce hot strength, and just the cost of composite adhesive is high more a lot of than sole binder.
The type material modification: in recent years, along with the novel material the reach of science, many investigators begin to attempt utilizing the property of novel material that waterglass adhesive is carried out modification.Utilize nano-oxide modified Portland tackiness agent such as Zhang Li etc., because nano-oxide is easy and the reaction of strong basicity tackiness agent, modified effect is not obvious, and cost is high.Xu Feng etc. utilize crystal whisker of hexa potassium titanate modified Portland tackiness agent, because the special construction of whisker, its bonding strength and water tolerance all are significantly improved, and intensity rises to 24.8MPa by 15.9MPa after the modification, and rate of increase is 55.97%.
Inorganic adhesive is a field of rising, can be used for the heat-resisting of the materials such as metal, glass-ceramic, timber and other and other functional bonding.The same with other inorganic materials, had uninflammability, thermotolerance, good endurance, the raw material advantage such as be easy to get, inorganic adhesive discharges without any VOC in addition, and very safety and environmental protection more and more receives common people's concern at present.Existing inorganic adhesive mainly is divided into phosphoric acid salt and silicate two large series.Phosphate-based inorganic glue is too crisp, heat resisting temperature not high (about 900 ℃), unsuitable plane adhesion; And the cost of silicate inorganic glue is minimum, operating procedure is the simplest, the industrial application amount maximum, so study on the modification to silicate adhesive, have very important social value and realistic meaning, the silicate inorganic glue selects water-soluble alkali metal silicates to make sizing mostly, although plane adhesion intensity and thermotolerance aspect are improved, but water tolerance is very poor, can not be used for the bonding of high humidity environment.
Summary of the invention
Technical problem solved by the invention is to provide a kind of preparation method of modified Portland inorganic adhesive, to solve the shortcoming in the above-mentioned background technology.
Technical scheme of the present invention is:
A kind of modified Portland inorganic adhesive, its raw material comprises the component of following weight part:
Quartz sand: 4-8 part
Silicon carbide: 2-3 part
Massfraction is the potassium silicate aqueous solution of 35-55%: 110-140 part;
Cellulose acetate: 16-24 part;
Acetone: 20-30 part;
Tolylene diisocyanate: 3-6 part
Hexa-methylene-1,6 vulcabond: 1-3 part
Dimethylol propionic acid: 1-2 part
Dihydroxy-benzene propionic acid: 1-3 part
DMF: 5-8 part;
Dibutyl tin laurate: 0.06-0.09 part;
Dipropyl amine: 4-5 part;
Bariumchloride: 0.8-1.3 part;
Calcium stearate: 5-9 part;
Deionized water: 25-48 part
The preparation method of above-mentioned modified Portland inorganic adhesive may further comprise the steps:
1) quartz sand and silicon carbide are clayed into power, excessively for subsequent use behind the 200 order sub-sieves;
2) take by weighing the acetone of 20-30 weight part, then add therein the cellulose acetate of 16-24 weight part, fully stirred 15-45 minute, make cellulose acetate solution, seal for subsequent use;
3) with the dimethylol propionic acid of 1-2 weight part, dihydroxy-benzene propionic acid and the 5-8 weight part N of 1-3 weight part, dinethylformamide joins in the 250ml round-bottomed flask of drying nitrogen protection, fully stirred 10-20 minute, add the tolylene diisocyanate of 3-6 weight part, the hexa-methylene-1 of 1-3 weight part, the dibutyl tin laurate of 6 vulcabond and 0.06-0.09 weight part, at 75-100 ℃ of lower stirring reaction 60-180 minute, solvent is sloughed in underpressure distillation, makes base polyurethane prepolymer for use as;
4) base polyurethane prepolymer for use as that step 3) is made joins in the By Amine Solutions that the deionized water of the dipropyl amine of 4-5 weight part and 25-48 weight part is mixed with, high-speed stirring, under room temperature emulsification 30-90 minute; Add again the cellulose acetate solution of step 1) preparation, under agitation in 65-90 ℃ of emulsion reaction 90-150 minute, obtain the cellulose acetate emulsion;
5) massfraction that the cellulose acetate emulsion that step 4) is prepared joins the 110-140 weight part is in the potassium silicate aqueous solution of 35-55%, at 75-95 ℃ of lower stirring reaction 60-120 minute, the calcium stearate and quartz sand powder that 4-8 weight part step 1) makes and the silicon carbide powder of 2-3 weight part that then add bariumchloride, the 5-9 weight part of 0.8-1.3 weight part, after fully stirring again 45-65 ℃ of reaction 40-55 minute.
Principle of the present invention and effect: select an amount of quartz sand, silicon carbide as filler, have higher physical strength, heat-resisting and water tolerance preferably, and the performances such as shrinking percentage can reduce adhesive solidification the time, modified effect is remarkable, cost is low, and easily operation construction.And cellulose acetate is part of hydroxyl in the Mierocrystalline cellulose product after by acetic acid esterified, contains great amount of hydroxy group and ethanoyl isopolarity group on the molecular chain, its good mechanical performance, and low toxicity, low combustion, water resisting property is good, uses very extensive.The present invention at first utilizes self-emulsifying emulsifier-free emulsion polymerization method to prepare the cellulose acetate emulsion, then by the complexing salt-forming reaction between acetate ion, stearate radical ion and the alkali metal cation, in Molecular Structure of Silicates, introduce the cellulose macromolecule chain, and capture alkali metal cation, can reduce simultaneously the fragility of solidification of silicon hydrochlorate and improve its water repelling property, the filler that adds again optimized choice obtains pliable and tough anti-water silicate tackiness agent.The modified Portland inorganic adhesive snappiness that the present invention makes is good, water-fast, bonding force is strong, nontoxic, environmental protection, and also preparation technology is fairly simple, is suitable for industrialization promotion and production.
Embodiment
Following examples describe the present invention in detail.Various raw material used in the present invention and items of equipment are conventional commercially available prod, all can buy directly by market to obtain.
Embodiment 1:
1) quartz sand and silicon carbide are clayed into power, excessively for subsequent use behind the 200 order sub-sieves;
2) take by weighing the acetone of 20 weight parts, then add therein the cellulose acetate of 16 weight parts, fully stirred 15 minutes, make cellulose acetate solution, seal for subsequent use;
3) with the dimethylol propionic acid of 1 weight part, dihydroxy-benzene propionic acid and the 5 weight part N of 1 weight part, dinethylformamide joins in the 250ml round-bottomed flask of drying nitrogen protection, fully stirred 10 minutes, add the tolylene diisocyanate of 3 weight parts, the hexa-methylene-1 of 1 weight part, the dibutyl tin laurate of 6 vulcabond and 0.06 weight part, 75-100 ℃ of lower stirring reaction 60 minutes, solvent was sloughed in underpressure distillation, makes base polyurethane prepolymer for use as;
4) base polyurethane prepolymer for use as that step 3) is made joins in the By Amine Solutions that the deionized water of the dipropyl amine of 4 weight parts and 25 weight parts is mixed with, high-speed stirring, and emulsification is 30 minutes under room temperature; The cellulose acetate solution that adds again step 1) preparation under agitation in 65 ℃ of emulsion reactions 90 minutes, obtains the cellulose acetate emulsion;
5) massfraction that the cellulose acetate emulsion of step 4) preparation is joined 110 weight parts is in 35% the potassium silicate aqueous solution, 75 ℃ of lower stirring reactions 60 minutes, the calcium stearate and quartz sand powder that 4 weight part step 1) make and the silicon carbide powder of 2 weight parts that then add bariumchloride, 5 weight parts of 0.8 weight part, after fully stirring again 45 ℃ of reactions 40 minutes.
Embodiment 2:
1) quartz sand and silicon carbide are clayed into power, excessively for subsequent use behind the 200 order sub-sieves;
2) take by weighing the acetone of 25 weight parts, then add therein the cellulose acetate of 20 weight parts, fully stirred 30 minutes, make cellulose acetate solution, seal for subsequent use;
3) with the dimethylol propionic acid of 1 weight part, dihydroxy-benzene propionic acid and the 6 weight part N of 2 weight parts, dinethylformamide joins in the 250ml round-bottomed flask of drying nitrogen protection, fully stirred 15 minutes, add the tolylene diisocyanate of 5 weight parts, the hexa-methylene-1 of 2 weight parts, the dibutyl tin laurate of 6 vulcabond and 0.08 weight part, 80 ℃ of lower stirring reactions 100 minutes, solvent was sloughed in underpressure distillation, makes base polyurethane prepolymer for use as;
4) base polyurethane prepolymer for use as that step 3) is made joins in the By Amine Solutions that the deionized water of the dipropyl amine of 5 weight parts and 40 weight parts is mixed with, high-speed stirring, and emulsification is 65 minutes under room temperature; The cellulose acetate solution that adds again step 1) preparation under agitation in 75 ℃ of emulsion reactions 120 minutes, obtains the cellulose acetate emulsion;
5) massfraction that the cellulose acetate emulsion of step 4) preparation is joined 120 weight parts is in 45% the potassium silicate aqueous solution, 85 ℃ of lower stirring reactions 100 minutes, the calcium stearate and quartz sand powder that 6 weight part step 1) make and the silicon carbide powder of 2 weight parts that then add bariumchloride, 7 weight parts of 1.1 weight parts, after fully stirring again 55 ℃ of reactions 50 minutes.
Embodiment 3:
1) quartz sand and silicon carbide are clayed into power, excessively for subsequent use behind the 200 order sub-sieves;
2) take by weighing the acetone of 30 weight parts, then add therein the cellulose acetate of 24 weight parts, fully stirred 45 minutes, make cellulose acetate solution, seal for subsequent use;
3) with the dimethylol propionic acid of 2 weight parts, dihydroxy-benzene propionic acid and the 8 weight part N of 3 weight parts, dinethylformamide joins in the 250ml round-bottomed flask of drying nitrogen protection, fully stirred 20 minutes, add the tolylene diisocyanate of 6 weight parts, the hexa-methylene-1 of 3 weight parts, the dibutyl tin laurate of 6 vulcabond and 0.09 weight part, 100 ℃ of lower stirring reactions 180 minutes, solvent was sloughed in underpressure distillation, makes base polyurethane prepolymer for use as;
4) base polyurethane prepolymer for use as that step 3) is made joins in the By Amine Solutions that the deionized water of the dipropyl amine of 5 weight parts and 48 weight parts is mixed with, high-speed stirring, and emulsification is 90 minutes under room temperature; The cellulose acetate solution that adds again step 1) preparation under agitation in 90 ℃ of emulsion reactions 150 minutes, obtains the cellulose acetate emulsion;
5) massfraction that the cellulose acetate emulsion of step 4) preparation is joined 140 weight parts is in 55% the potassium silicate aqueous solution, 95 ℃ of lower stirring reactions 120 minutes, the calcium stearate and quartz sand powder that 8 weight part step 1) make and the silicon carbide powder of 3 weight parts that then add bariumchloride, 9 weight parts of 1.3 weight parts, after fully stirring again 65 ℃ of reactions 55 minutes.
Foregoing description only proposes as the enforceable technical scheme of the present invention, not as the Single restriction condition to its technical scheme itself.
Claims (1)
1. the preparation method of a modified Portland inorganic adhesive is characterized in that: may further comprise the steps:
1) quartz sand and silicon carbide are clayed into power, excessively for subsequent use behind the 200 order sub-sieves;
2) take by weighing the acetone of 20-30 weight part, then add therein the cellulose acetate of 16-24 weight part, fully stirred 15-45 minute, make cellulose acetate solution, seal for subsequent use;
3) with the dimethylol propionic acid of 1-2 weight part, dihydroxy-benzene propionic acid and the 5-8 weight part N of 1-3 weight part, dinethylformamide joins in the 250ml round-bottomed flask of drying nitrogen protection, fully stirred 10-20 minute, add the tolylene diisocyanate of 3-6 weight part, the hexa-methylene-1 of 1-3 weight part, the dibutyl tin laurate of 6 vulcabond and 0.06-0.09 weight part, at 75-100 ℃ of lower stirring reaction 60-180 minute, solvent is sloughed in underpressure distillation, makes base polyurethane prepolymer for use as;
4) base polyurethane prepolymer for use as that step 3) is made joins in the By Amine Solutions that the deionized water of the dipropyl amine of 4-5 weight part and 25-48 weight part is mixed with, high-speed stirring, under room temperature emulsification 30-90 minute; Add again the cellulose acetate solution of step 1) preparation, under agitation in 65-90 ℃ of emulsion reaction 90-150 minute, obtain the cellulose acetate emulsion;
5) massfraction that the cellulose acetate emulsion that step 4) is prepared joins the 110-140 weight part is in the potassium silicate aqueous solution of 35-55%, at 75-95 ℃ of lower stirring reaction 60-120 minute, the calcium stearate and quartz sand powder that 4-8 weight part step 1) makes and the silicon carbide powder of 2-3 weight part that then add bariumchloride, the 5-9 weight part of 0.8-1.3 weight part, after fully stirring again 45-65 ℃ of reaction 40-55 minute.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106918467A (en) * | 2017-04-14 | 2017-07-04 | 长庆石油勘探局技术监测中心 | A kind of method for successively gathering iron-based material corrosion product |
| CN114248342A (en) * | 2022-02-07 | 2022-03-29 | 东莞市志橙半导体材料有限公司 | Preparation method of special-shaped semiconductor tube core non-conductive protection tube |
| CN116063687A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrophobic quartz sand and preparation method and application thereof |
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| CN101921565A (en) * | 2010-08-31 | 2010-12-22 | 黑龙江省科学院石油化学研究院 | Preparation method of solvent-free and high temperature-resistant adhesive |
| CN102079957A (en) * | 2010-12-09 | 2011-06-01 | 深圳市库泰克电子材料技术有限公司 | Low-temperature rapidly-curable surface mounting adhesive |
| CN102863907A (en) * | 2012-10-17 | 2013-01-09 | 中南林业科技大学 | Flexible water-resistant silicate wood adhesive and preparation method thereof |
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Patent Citations (4)
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| JP2002194317A (en) * | 2000-12-26 | 2002-07-10 | Oshika:Kk | Adhesive composition having high water resistance |
| CN101921565A (en) * | 2010-08-31 | 2010-12-22 | 黑龙江省科学院石油化学研究院 | Preparation method of solvent-free and high temperature-resistant adhesive |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106918467A (en) * | 2017-04-14 | 2017-07-04 | 长庆石油勘探局技术监测中心 | A kind of method for successively gathering iron-based material corrosion product |
| CN116063687A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrophobic quartz sand and preparation method and application thereof |
| CN116063687B (en) * | 2021-11-01 | 2024-05-07 | 中国石油化工股份有限公司 | Hydrophobic quartz sand and preparation method and application thereof |
| CN114248342A (en) * | 2022-02-07 | 2022-03-29 | 东莞市志橙半导体材料有限公司 | Preparation method of special-shaped semiconductor tube core non-conductive protection tube |
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Application publication date: 20130424 |