CN1167756C - Stone protecting agent and its preparation method - Google Patents
Stone protecting agent and its preparation method Download PDFInfo
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- CN1167756C CN1167756C CNB011235527A CN01123552A CN1167756C CN 1167756 C CN1167756 C CN 1167756C CN B011235527 A CNB011235527 A CN B011235527A CN 01123552 A CN01123552 A CN 01123552A CN 1167756 C CN1167756 C CN 1167756C
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Abstract
The present invention relates to a stone protective agent which comprises a perfluoromacromolecular polymer. The monomer of the polymer comprises the components by the weight proportion: 40 to 90% of monomer I, 1 to 18% of silicon-containing monomer II, 2 to 50% of monomer III and an alkenyl polymer monomer IV except for the polymer monomers I, II and III. The polymer monomers are polymerized in solution under the condition of initiator existence. The dosage of an initiator is from 0.1 to 2%, and used solvent is one of ketone solvent, ester solvent and alcohol solvent. The addition of the solvent is from 100 to 300%. The perfluoromacromolecular stone protective agent has a solvent type or a water soluble type. Different stones treated by the stone protective agent have the good effects of water resistance and oil resistance in different environments. The stone protective agent has the advantages of simple coating method and proper manufacturing condition and can be suitable for natural or artificial stones, such as marbles, granite, sandstones, tiles, cement, ceramics, gypsum, etc.
Description
The present invention relates to a kind of Stone Protection Agent And Manufacturing Method.Its product can be used for marble, grouan, sandstone, brick and tile, cement, pottery, gypsum and artificial stone-like material's waterproof, antifouling and grease proofing.
Material of construction is stone material particularly, use extremely wide, but stone material in use, frequent water absorption character and air environmental pollution because of self, chemical corrosion, the liver moss lichens corrodes, the frost crowfoot cracks, the daylight long-term irradiation, the summer in winter cold and hot repeatedly alternately and multiple natural cause such as rain drop erosion destroy and generation rust staining, Bai Hua, water stain, greasy dirt even break.The appearance of these illnesss disappears the load-bearing of building materials such as stone material or decorate properties, causes permanent sorry.
The protection of building materials such as stone material needs just have anti-water, anti-oily, antifouling characteristic after the disposable processing of building materials, and when being used for outdoor exposing, protective material itself also should have the function of uvioresistant long-term irradiation.Make building materials such as stone material have the method and the existing report of product of water resistance, the emulsifying agent that its use organic polymer base-material silicone oil of Chinese patent 94111337.X " organic silicon water-proof paint and production technique thereof ", water, sim alkylphenol Soxylat A 25-7 or maleic anhydride derivative or both mixed solutions are made, though this product good water-proof effect and the ventilation property that does not hinder stone material, it can not prevent greasy dirt.Japanese Patent JP 05421745 utilizes paraffin wax to make the curing agent of waterproof layer, and it forms one deck sealing membrane continuously at stone surface, and the pore of sealing base material is not so possess ventilation property.
Fluorinated copolymer can have the water of refusing simultaneously, refuse oily ability, utilize this characteristic of fluoro containing polymers to handle textiles, paper, leathers etc. make it have anti-water, the existing report of the technical scheme of anti-functional oil, United States Patent (USP) 4,127,711 " fluorine-containing terpolymers " are pointed out, the perfluor aliphatics acrylic or methacrylic acid mono that contains weight percent 55～80%, with 15～35% acrylic or methacrylic acid polyoxyethylene ester monomer, and 1～15% the acrylic or methacrylic acid dialkyl amine ester or the terpolymer of corresponding amines or quaternary amine, be applied to the softish textiles, on the leather, can improve the anti-water of its product effectively, oil-resistant characteristic, but this patent and be not suitable for the permanent waterproof of building materials such as crust stone material, anti-oil treatment.About report also being arranged with (per) fluoropolymer protection stone material; Chinese patent 89102813.7 " the PFPE protection building stones of water microemulsion form are avoided weathering " has been introduced a kind of protective agent that applies on building materials such as stone material; this protective agent comprises the microemulsion of the PFPE that contains the perfluoroalkyl terminal group; it is used to protect stone material and avoids atmospheric corrosion; but the fluorine-containing latex of this treatment process; stability is limited, and we find that it will could prepare this milk sap, the use inconvenience before base material applies.
The invention reside in the weak point of avoiding prior art to exist, provide to be suitable for the stone surface processing, make stone material have durable water resistant, grease proofing, antifouling ability, and the easy a kind of Stone Protection Agent And Manufacturing Method of application process.
Embodiment of the present invention are: this stone protecting agent is made of the perfluor high molecular polymer, and its polymer monomer and weight percent ratio are:
A, at least a molecular formula are the monomer I of I, and add-on is the 40-90% of polymer monomer gross weight:
Wherein: R
fBe to contain C
2-20Straight or branched perfluor functional group;
R is hydrogen or methyl;
A is O or NR
2R wherein
2Represent hydrogen or methyl;
R
1Be C
1-15Alkylidene group.
The per-cent that I type polymer monomer accounts for the polymer monomer gross weight should surpass this ratio and then cause dispersive ability to descend less than 90%.
52～87% content is proper, and so stability, solvability are closed anti-water enduring quality and reached well balanced.
B, at least a molecular formula are the silicon-containing monomer II of II, and add-on is the 1-18% of polymer monomer gross weight:
Wherein: R
3Be hydrogen or methyl or fluorine or chlorine;
Q is C
1-4Alkylidene group;
Y is a methyl or methoxy.
C, at least a molecular formula are the monomer II I of III, and add-on is the 2-50% of polymer monomer gross weight:
Wherein: R
4Be hydrogen or methyl;
R
5Or R
6Be separate hydrogen or C
1-4Alkyl;
X：2-4。
III class amine-containing polymer monomer provides the dispersion stabilization of product, and preferred weight percent is 10～35%
D. remove molecular formula I, II, alkenyl polymer monomer I V beyond the III polymer monomer, this alkenyl polymer monomer I V is selected from a kind of of following material: ethene, propylene, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, (methyl) ethyl propenoate, the vinylformic acid laurate, vinylchlorid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinyl pyrrolidone, vinylbenzene, Vinylstyrene, acrylamide, N hydroxymethyl acrylamide, a kind of in (methyl) vinyl cyanide or (methyl) glycidyl acrylate, add-on is 5～30% of a polymer monomer total amount;
IV type monomer can provide sticking power, hardness, film-forming properties and the bridging property of product, can give its stability in wideer pH value scope.Can also cooperate the consistency that improves polymkeric substance and solvent with solvent, and reduce product cost.
Above-mentioned polymer monomer carries out solution polymerization jointly in the presence of initiator, initiator amount is 0.1～2% of a polymer monomer gross weight; The solvent that described solution polymerization is adopted is a kind of of ketone, ester, alcoholic solvent, includes water-soluble and water-immiscible solvent, and this solution add-on is 100～300% of a polymer monomer weight.
The manufacture method of described stone protecting agent is: adopt the solution polymerization step; polymer monomer I, II, III, IV and solvent are added polymerization reaction kettle by proportioning; add initiator simultaneously; under agitation carry out polymerization; stirring velocity is 60～500 rev/mins; temperature of reaction is lower than the boiling temperature of solvent for use, and 3～10 hours reaction times obtained polymkeric substance, and this polymeric articles is the solvent-borne type stone protecting agent.
As in the manufacture method of stone protecting agent; institute's solubilizing agent is a water-immiscible solvent; behind polymerization procedure; carry out solvent removed by evaporation at reduced pressure; make the polymer residue quantity of solvent less than 2% of polymerisate weight; add salifiable acid solution then, the product that obtains with this method is water-soluble type stone protecting agent.
As in the manufacture method of stone protecting agent, institute's solubilizing agent is water-soluble solvent, can directly add salifiable acid solution behind polymerization procedure, and the product that obtains with this method is water-soluble type stone protecting agent.
The present invention still has following attached technical characterictic, and in the polymkeric substance proportioning, described molecular formula II monomer is: trimethyl silyl methylene radical 2-propenyl chloride acid esters [CH
2=CClCOOCH
2Si (CH
3)
3] or trimethoxysilyl methylene radical acrylate [CH
2=CHCOOCH
2Si (OCH
3)
3] or trimethyl silyl methylene radical (methyl) acrylate [CH
2=C (CH
3) COOCH
2Si (CH
3)
3].
Described initiator is selected a kind of in the following compounds for use: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, peroxidation diisopropyl ester, di-cyclohexylperoxy dicarbonate or with dibenzoyl peroxide and N, the redox system that the N xylidine constitutes.
Can add chain-transfer agent in polymer monomer, used chain-transfer agent is selected a kind of in Dodecyl Mercaptan, tetracol phenixin or the carbon tetrabromide for use, and add-on is 0.05～1% of a polymer monomer gross weight.
Described solution polymerization solvent for use is selected from a kind of in acetone, butanone, ethylene glycol monoemethyl ether, hexone, N-BUTYL ACETATE, vinyl acetic monomer, the Virahol.
After using water-soluble solvent to carry out polymerization; or use water-immiscible solvent to carry out polymerization and steam desolventize after; in resulting polymers, also can add a kind of in the following salifiable acids; the optional hydrochloric acid of salifiable acids, alkylsurfuric acid, phosphoric acid, oxyacetic acid, formic acid or acetate; use be weight percentage 1～20% acid solution of concentration; making polymkeric substance become water-soluble salt with acid-respons, is that dispersion medium obtains water-soluble stone protecting agent with water.The acid solution add-on is 100～300% of a polymerisate.
In the manufacture method of described stone protecting agent, institute's solubilizing agent is a water-immiscible solvent, behind polymerization procedure, carries out solvent removed by evaporation at reduced pressure, makes the polymer residue quantity of solvent less than 2% of polymerisate weight, adds salifiable acid solution then.
In the manufacture method of described stone protecting agent, when institute's solubilizing agent is water-soluble solvent, behind polymerization procedure, directly add salifiable acid solution.
The present invention has following advantage compared to existing technology: this perfluor polymer stone protecting agent has very low surface tension; can be evenly distributed on the porous stone micro-pore wall; and form efficiently waterproof, anti-oil reservoir; the water or the oil droplet that drop on the substrate surface are not oozed down as the droplet on the lotus leaf, and water can be more than 100 degree at the contact angle on surface.Compared with former method, stone material by this solvent-borne type or water-soluble (per) fluoropolymer product treatment has better to be refused water, refuses oily effect, can stop the intrusion of moisture or dirt effectively, in the alternate cycles of freezing, thawing, it is stable that dispersing property keeps, insensitive to atmospheric moisture, so extraneous bigger interionic reactive force is also very little to its influence, therefore performance is also kept under the hard water environment, does not also worry foaming or peeling.Owing to be attached to product of the present invention on the micro-pore wall, do not pile up and stop up the stone material micropore, so can keep the moisture at stone material inside and back to ooze out, have the good permeability of " freely breathing ".The multipolymer of this perfluorinated monomers can be dispersed in solvent or the water and need not add other tensio-active agents.The content of the volatilizable thing of water-soluble type polymkeric substance is very low, and is functional under high-shear and high temperature, stable.This stone protecting agent can adapt to natural and artificial stone-like materials such as various hard surfaces, particularly marble, grouan, sandstone, brick and tile, cement, pottery or gypsum, can obviously improve their wearing qualities under outdoor severe weather and various adverse environment.Reaction conditions was relatively gentleer when stone protecting agent was made, need not high temperature, high pressure.Using method is also fairly simple, applies operation and can not produce destruction to the stone surface outward appearance, need not also needn't can adopt to spray or brush with brush, sponge or cloth through Overheating Treatment.
With embodiment the technology of the present invention embodiment is described below,
Embodiment 1: the % of following prescription is weight percentage,
With 60 gram perfluoro propyl dimethylene acrylate [CH
2=CH-COO (CH
2)
2(CF
2)
2CF
3], 10 gram trimethyl silyl acrylate, 15 gram dimethylaminoethyl methacrylate, 5 gram vinyl pyrrolidones and 10 gram methyl methacrylates, 0.5 gram Diisopropyl azodicarboxylate, 150 gram hexones, 0.2 gram lauryl mercaptan evenly add in 500 milliliters of reactors, agitator, thermometer, reflux exchanger, constant pressure funnel are housed in the reactor, reactor places 90 ℃ constant temperature heating device, and reaction is 5 hours under 60 rev/mins of stirrings.Be cooled to room temperature then, discharging, getting polymerisate is the solvent-borne type stone protecting agent.
This solvent-borne type stone protecting agent is applied to different lithotomes surface, measures water, oil is at the contact angle on surface, as following table, construction processing surface standard usage quantity be 100 grams/square metre.
The liquid-solid contact angle of table 1 (degree)
| Water | Valelinum Liquidum | |
| Baoxing is white | 95 | 65 |
| Chinese red | 105 | 65 |
| The grouan fired slab | 105 | 68 |
Experimental result shows for different stone material polymer liquid all excellent protection, even if oil does not soak into yet.
The liquid of will constructing is applied to different lithotomes surface, construction processing surface use the amount of construction liquid be 100 grams/square metre, measure protectiveness to various spots, test uses standard to be GB/T3910.14-1999 result such as table 2:
Table 2
Annotate: "+" is expressed as that stone material is capable of washing after source of pollution pollute 24 hours totally to leave no trace.
Experimental result shows that stone surface has good stain resistance after treatment.
The liquid of will constructing is applied to marble surface, the usage quantity on processed surface be 100 the gram/square metre, carry out accelerated weathering test, the test use standard to be GB/T16529-1996, result such as table 3.
Table 3
| Sample | Water-intake rate before handling | Handle the back water-intake rate | 250 hours aging back water-intake rates |
| Chinese red | 0.56％ | 0.026％ | 0.031％ |
The result shows that product of the present invention has good anti-water permeate and good anti-environmental aging ability.
Embodiment 2 (% is weight percentage in the following prescription):
With 100 gram perfluoro butyl dimethylene (methyl) acryloyl methylamine [CH
2=C (CH
3)-CON (CH
3) (CH
2)
2(CF
2)
3CF
3], 20 gram trimethoxysilyl tetramethylene acrylate, 30 gram dimethylin dimethylene acrylate, initiator 1 gram dibenzoyl peroxide and 1 gram N, N xylidine, 300 gram acetone solvents evenly add 1000 milliliters of reactors, do not add alkenyl polymer monomer and chain-transfer agent.Reactor assembly agitator, thermometer, reflux exchanger, constant pressure funnel, reacting appliance have the heating unit of 50 ℃ of constant temperature, and reaction is 10 hours under 100 rev/mins of stirrings.Adding 100 gram concentration then is 10% aqueous formic acid, and this polymkeric substance is continued the insulation 1 hour that refluxes, and is cooled to the room temperature discharging, polymerisate is water-soluble type stone protecting agent.
Embodiment 3 (% is weight percentage in the following prescription):
With 80 gram perfluoro capryl tetramethylene (methyl) acrylate [CH
2=C (CH
3)-COO (CH
2)
4(CF
2)
7CF
3], 18 gram trimethyl silyl methylene radical acrylate, 10 gram dimethylin tetramethylene acrylate and 30 gram diethylin tetramethylene acrylate, 40 gram Hydroxyethyl acrylates, 0.5 gram Diisopropyl azodicarboxylate, 100 gram solvent Virahols evenly add 1000 milliliters of reactors, reactor assembly agitator, thermometer, reflux exchanger, constant pressure funnel, reacting appliance has the heating unit of 83 ℃ of constant temperature, and polyreaction is 3 hours under 300 rev/mins stirring.Adding 200 gram concentration are 20% aqueous hydrochloric acid, and this polymeric solution is refluxed is incubated 1 hour, is cooled to the room temperature discharging then, and getting polymerisate is water-soluble type stone protecting agent.
Embodiment 4 (% is weight percentage in the following prescription):
With 71 gram perfluoro propyl dimethylene acrylate [CH
2=CH-COO (CH
2)
2(CF
2)
2CF
3], 18 gram trimethyl silyl acrylate, 18 gram dimethylaminoethyl methacrylate, 8 gram butyl methacrylate, 0.5 gram dibenzoyl peroxide, 100 gram hexones, 0.2 gram lauryl mercaptan evenly add in 500 milliliters of reactors.Reactor assembly agitator, thermometer, reflux exchanger, constant pressure funnel, reacting appliance have the heating unit of 90 ℃ of constant temperature, after reacting 5 hours under 100 rev/mins of stirrings.The reduced vacuum degree maintains 600～700 mmhg and the solvent steaming can be removed, and recording solvent residual amount is following end underpressure distillation about 3 grams.Adding 300 gram concentration are 2% acetic acid aqueous solution, and this polymkeric substance is continued to be incubated half an hour, are cooled to room temperature, discharging then, and getting polymerisate is water-soluble type stone protecting agent.
10 parts of polymerisates are joined in 40 parts of water, and preparation construction liquid is applied to different lithotomes surface with the construction liquid for preparing, and measures water, and oil is at the contact angle on surface.The usage quantity standard on processed surface be 100 the gram/square metre
Table 4 construction liquid and treat surface contact angle (degree)
| Water | Valelinum Liquidum | |
| Baoxing is white | 97 | 67 |
| Chinese red | 106 | 67 |
| The grouan fired slab | 108 | 69 |
The result shows for different stone material polymer liquid all favorable protection, even if oil does not soak into yet.
Embodiment 5 (% is weight percentage in the following prescription):
With 85 gram perfluoro butyl dimethylene (methyl) acryloyl methylamine [CH
2=C (CH
3) CON (CH
3) (CH
2)
2(CF
2)
3CF
3], 10 gram trimethyl silyl tetramethylene 2-propenyl chloride acid esters [CH
2=CClCOO (CH
2)
4Si (CH
3)
3], 10 gram diethyl amido dimethylene acrylate, 1 gram dibenzoyl peroxide initiator, 150 gram N-BUTYL ACETATE solvents, and be added with chain-transfer agent 1 gram tetracol phenixin, evenly add 500 milliliters of reactors, reactor assembly agitator, thermometer, reflux exchanger, constant pressure funnel, reacting appliance has the heating unit of 85 ℃ of constant temperature, stirs under the 300 commentaries on classics conditions at per minute and reacts 3 hours.Vacuumize then, vacuum tightness maintains 600～700 mmhg and gets final product, when 98% solvent steamed remove after; adding 300 gram concentration again is 2% acetic acid solution; this polymerisate backflow is incubated half an hour, is cooled to the room temperature discharging, get polymerisate-water-soluble type stone protecting agent.
Per-cent all is weight percentage described in this specification sheets.
Claims (9)
1, a kind of stone protecting agent includes the perfluor high molecular polymer, it is characterized in that polymer monomer and weight percent are:
A, at least a molecular formula are the monomer I of I, and add-on is the 40-90% of polymer monomer gross weight:
Wherein: R
fBe to contain C
2-20Straight or branched perfluor functional group;
R is hydrogen or methyl;
A is O or NR
2R wherein
2Represent hydrogen or methyl;
R
1Be C
1-15Alkylidene group;
B, at least a molecular formula are the silicon-containing monomer II of II, and add-on is the 1-18% of polymer monomer gross weight:
Wherein: R
3Be hydrogen or methyl or fluorine or chlorine;
Q is C
1-4Alkylidene group;
Y is a methyl or methoxy;
C, at least a molecular formula are the monomer II I of III, and add-on is the 2-50% of polymer monomer gross weight:
Wherein: R
4Be hydrogen or methyl;
R
5And R
6Be separate hydrogen or C
1-4Alkyl;
x：2-4
D, remove molecular formula I, II, alkenyl polymer monomer I V beyond the III polymer monomer, this alkenyl polymer monomer I V is selected from a kind of of following material: ethene, propylene, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, the vinylformic acid laurate, vinylchlorid, vinyl pyrrolidone, vinylbenzene, Vinylstyrene, acrylamide, N hydroxymethyl acrylamide, a kind of in (methyl) vinyl cyanide or (methyl) glycidyl acrylate, add-on is 5～30% of a polymer monomer total amount;
Above-mentioned polymer monomer carries out solution polymerization jointly in the presence of initiator, initiator amount is 0.1～2% of a polymer monomer gross weight; The solvent that described solution polymerization is adopted is a kind of of ketone, ester, alcoholic solvent, and this solution add-on is 100～300% of a polymer monomer gross weight.
2, the described stone protecting agent of claim 1 is characterized in that described molecular formula is that the monomer II of II is trimethyl silyl methylene radical 2-propenyl chloride acid esters or trimethoxy silicomethane methylene radical acrylate or trimethyl silyl methylene radical (methyl) acrylate.
3, the stone protecting agent according to claim 1; it is characterized in that described initiator selects a kind of in the following compounds for use: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, peroxidation diisopropyl ester, di-cyclohexylperoxy dicarbonate or dibenzoyl peroxide and N, the redox that the N xylidine constitutes embodies system.
4, the stone protecting agent according to claim 1; it is characterized in that in polymer monomer, can adding chain-transfer agent; described chain-transfer agent is selected a kind of in Dodecyl Mercaptan, tetracol phenixin or the carbon tetrabromide for use, and add-on is 0.05～1% of a polymer monomer gross weight.
5, the stone protecting agent according to claim 1 is characterized in that described solution polymerization solvent for use is selected from a kind of in acetone, butanone, ethylene glycol monoemethyl ether, hexone, N-BUTYL ACETATE, vinyl acetic monomer, the Virahol.
6, the stone protecting agent according to claim 1; it is characterized in that after using water-soluble solvent to carry out polymerization or use water-immiscible solvent to carry out polymerization and steam desolventize after; in the gained polymerisate, also can add a kind of in the following salifiable acids; salifiable acids is hydrochloric acid, alkylsurfuric acid, phosphoric acid, oxyacetic acid, formic acid or acetate; 1～20% the acid solution of using that concentration is weight percentage; make polymkeric substance become water-soluble salt, the acid solution add-on is 100～300% of a polymer monomer gross weight.
7, the manufacture method of the described stone protecting agent of a kind of claim 1; it is characterized in that its polymerization procedure is: polymer monomer I, II, III, IV and solvent are added polymerization reaction kettle by proportioning; add initiator simultaneously; under agitation carry out polymerization; stirring velocity is 60～500 rev/mins; temperature of reaction is lower than the boiling temperature of solvent for use, the reaction times: obtained polymkeric substance in 3～10 hours, this polymkeric substance is the solvent-borne type stone protecting agent.
8, according to the manufacture method of the described stone protecting agent of claim 7; it is characterized in that institute's solubilizing agent is a water-immiscible solvent; behind polymerization procedure; carry out solvent removed by evaporation at reduced pressure; make the polymer residue quantity of solvent less than 2% of total polymer weight; add salifiable acid solution then, the polymkeric substance that obtains is the aqueous solution type stone protecting agent.
9, according to the manufacture method of the described stone protecting agent of claim 7, it is characterized in that institute's solubilizing agent is water-soluble solvent, behind polymerization procedure, add salifiable acid solution, the polymkeric substance that obtains is water-soluble type stone protecting agent.
Priority Applications (1)
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|---|---|---|---|
| CNB011235527A CN1167756C (en) | 2001-08-01 | 2001-08-01 | Stone protecting agent and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011235527A CN1167756C (en) | 2001-08-01 | 2001-08-01 | Stone protecting agent and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1400260A CN1400260A (en) | 2003-03-05 |
| CN1167756C true CN1167756C (en) | 2004-09-22 |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701710A (en) * | 2012-06-03 | 2012-10-03 | 安庆市隆鑫建材有限公司 | Environment-friendly brick taking urban domestic sludge as raw material, and production method thereof |
| CN102701786A (en) * | 2012-06-17 | 2012-10-03 | 吴骏 | Water-based protective agent for stone and preparation method and application of protective agent |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070066780A1 (en) * | 2003-06-09 | 2007-03-22 | Akihiko Ueda | Masonry-treating agent |
| CN1295283C (en) * | 2004-09-03 | 2007-01-17 | 济南中化纺科技开发有限公司 | Multifunctional effective waterproof and corrosion-proof materials |
| CN101769051A (en) * | 2009-12-17 | 2010-07-07 | 张立安 | Method for manufacturing simulated stone covering layer by machine on building wall |
| CN104559607B (en) * | 2015-01-12 | 2017-02-22 | 赵茹 | Hydrophobic and oleophobic harbor engineering concrete protective agent and preparation method thereof |
-
2001
- 2001-08-01 CN CNB011235527A patent/CN1167756C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701710A (en) * | 2012-06-03 | 2012-10-03 | 安庆市隆鑫建材有限公司 | Environment-friendly brick taking urban domestic sludge as raw material, and production method thereof |
| CN102701786A (en) * | 2012-06-17 | 2012-10-03 | 吴骏 | Water-based protective agent for stone and preparation method and application of protective agent |
| CN102701786B (en) * | 2012-06-17 | 2013-10-16 | 吴骏 | Water-based protective agent for stone and preparation method and application of protective agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1400260A (en) | 2003-03-05 |
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Assignee: Jolywood (Suzhou) Solar Material Technology Co., Ltd. Assignor: Libao Chemical Building Material Co., Ltd., Wenling City Contract fulfillment period: 2008.12.29 to 2013.12.28 Contract record no.: 2009320000138 Denomination of invention: Stone protecting agent and its preparation method Granted publication date: 20040922 License type: Exclusive license Record date: 20090225 |
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Effective date of registration: 20110913 Address after: 215542 Chang Kun Industrial Park, 32, Sha Bang Town, Jiangsu, Qingnian Road, Changshou City Patentee after: Jolywood (Suzhou ) Sunwatt Co., Ltd. Address before: 317523 Zhejiang province Wenling City Zeguo town Changhong Road No. 48 Patentee before: ZHEJIANG REPOW HIGH-TECH BUILDING MATERIALS CO., LTD. |
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