CN1435437A - Process for preparing graft polyolefin/lamellar silicate composite nanomaterial - Google Patents
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Abstract
A process for preparing composite graft polyolefine-laminated silicate nano material includes adding the organically modified laminated silicate powder to powdered polyolefine, adding the mixture of two or more monomers including initiator, in-situ polymerization reaction for graft copolymerization of polyolefine and nano intercalation of laminated silicate, washing, drying and granulating. The resultant material can be used as the modifier, isolating additive, compatibilizer, filler, or adhesive of polyolefine plastics.
Description
Technical field
The present invention relates to a kind of polyolefine (PO) and two or more monomer soild-phase graft copolymer and have the preparation method of the graft polyolefin/lamellar silicate composite nanomaterial (Grafted polyolefine/layered silicate nanocomposites is called for short GPOSNC) of the silicate powder formation of nanometer laminated structure.
Background technology
The principal character of nano composite material (Nanocomposites) be a component in the compound system have at least one dimension with nano-scale (≤100nm) be evenly dispersed in another component matrix.The nano composite material that polymkeric substance and layered silicate are formed, its polymkeric substance forms even and firm combining with the silicate powder with nano-scale laminate structure, the nanophase specific surface area is big, there is special interaction, so its performance has the raising of highly significant than corresponding macroscopic view or micron order matrix material (for example traditional Inorganic Fillers Filled is polymer-modified), even qualitative leap appears, show brand-new performance or function.Since middle 1980s, the development of nano composite polymer/laminated silicate material has represented a wide path of improving existing macromolecular material performance and development novel material significantly.
Nano composite polymer/laminated silicate material has multiple preparation method, intercalation compounding or claim to embed composite algorithm and at home and abroad study at most wherein, tool use value and development prospect.This method is to utilize layered silicate (if you would take off soil, kaolin etc.) have the characteristics of nano-lamellar structure, with between the help interposed layer of monomer by organic modifiers (as the quaternary ammonium salts cats product etc.), and carry out home position polymerization reaction, or macromole, oligopolymer is at melt, solution, under the emulsion state, directly insert the interlayer of organic modified sheet silicate, finally obtaining complete isolating leafing nano composite material of nanometer lamella (ExifoliatedNanocomposites) or interlamellar spacing is the intercalated nano-composite (IntercalatedNanocomposites) of nano-scale.
Polyolefine (as polyethylene, polypropylene etc.) has excellent physical and mechanical properties and processing characteristics, and is simultaneously cheap, thereby obtained application more and more widely.Yet because its molecule is nonpolar, surface energy is low, thereby polyolefinic binding property, wettability, printing and dyeing, gas permeability and all relatively poor with the consistency of other material etc.These drawbacks limit the further expansion of its range of application.Polyolefine is compared with engineering plastics as general-purpose plastics simultaneously, and its modulus, intensity, toughness, thermotolerance etc. are all lower, can not satisfy the requirement that engineering is used.For these reasons, the modification of polyolefine material more and more is subjected to people's attention.By existing polyolefin plastics is carried out modification, can significantly improve its performance, widen its range of application and improve value-added content of product, will produce tremendous influence to the development that promotes macromolecular material and related industries.
Polyolefin modified have many methods, and wherein nano combined is the technology for modifying that newly-developed gets up.Analyze theoretically, the leafing type or the intercalation type nano composite material of polyolefine and laminar silicic acid salt formation, performance should significantly be better than common polyolefin plastics, but, because polyolefinic nonpolar, low surface energy and hydrophobic nature, poor with the consistency of inorganics, its molecular weight is difficult to more greatly to the interlayer motion simultaneously, so polyolefine is difficult to form effectively nano combined with laminated inorganic matter.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of graft polyolefin/lamellar silicate composite nanomaterial, this method can effectively solve the problems referred to above such as the consistency difference that exists in the polyolefin/lamellar silicate composite nanomaterial preparation and macromole intercalation difficulty, improve the consistency between polyolefine and the layered silicate, promote of intercalation and the combination of polyolefine macromole at the layered silicate interlayer, thus the polyolefin/lamellar silicate composite nanomaterial that obtained performance significantly improves than common polyolefin plastics.
The preparation method of a kind of graft polyolefin/lamellar silicate composite nanomaterial provided by the invention comprises the step of following order:
(1) in reactor, drops into a certain proportion of powdery polyolefin, organic modified sheet silicate, monomer mixture and initiator;
(2) stirring reaction under nitrogen protection, temperature is controlled at 20～150 ℃, and the reaction times is 0.5～5 hour;
(3) the reaction after product is through 60～80 ℃ of distilled water or deionized water repetitive scrubbing, and suction filtration under 50～90 ℃ of temperature dry 16～48 hours then, promptly gets the graft polyolefin/lamellar silicate composite nanomaterial powder;
(4) above-mentioned powder twin screw extruder granulation promptly obtains the graft polyolefin/lamellar silicate composite nanomaterial pellet.
The weight proportion of above-mentioned each raw material of reaction mixture is: 100 parts of polyolefine, 1～100 part of organic modified sheet silicate, 1～100 part of monomer mixture, 0.01～3.0 part of initiator.Wherein, polyolefine comprises polypropylene (PP), high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), LLDPE (LLDPE) and polyolefinic derivative such as chlorinatedpolyethylene (CPE) etc.; Organic modified sheet silicate comprises with the polynite of various organism intercalation modifyings or wilkinite, kaolin, talcum powder, mica powder etc.; Monomer mixture comprises two kinds of monomers at least, and must comprise at least a polar monomer, wherein monomer comprises maleic anhydride and ester, fumaric acid anhydride and ester thereof, vinylbenzene and derivative thereof, methacrylic acid and various methacrylic ester, vinylformic acid and various acrylate, vinyl cyanide, acrylamide, vinyl acetate, N-vinyl pyridine or long-chain unsaturated carboxylic acid such as oleic acid, linolic acid, undecylenic acid and ester thereof etc.; Initiator comprises peroxide initiator and various radical polymerization initiators such as redox system, azo-initiator thereof.
Principle of the present invention is: adding contains two or more monomeric mixture of initiator and makes it polymerization in the mixture of powdery polyolefin and layered silicate powder, graft copolymerization takes place in monomer on the molecular polyolefin chain on the one hand, the interlayer of monomer insertion layered silicate carries out in-situ polymerization on the other hand, the result makes good intercalation and the combination of formation between polyolefine and the layered silicate, and the mechanical property of the graft polyolefin/lamellar silicate composite nanomaterial of gained and other performances are significantly improved.
The GPOSNC of the present invention's preparation need not separate and further refining can the application.Its Application Areas is very wide, comprising: (1) is directly used in and makes various polyolefin plastic products, and its intensity, modulus, toughness and other pertinences can all significantly improve and improve than unmodified polyolefin plastics; (2) as polyolefine and other polymkeric substance expanding material of polar polymer blend particularly; (3) as the enhancing plasticized modifier of other plastics of Polyolefin and; (4) as the coupling agent or the interface modifier of other plastics of Polyolefin and and weighting agent, fortifying fibre; (5), improve the character such as polarity, hydrophilic and hydrophobic, reactivity on surface, thereby improve bonding, the printing on surface, painted, covering with paint, plating, performance such as antistatic as the surface-modifying agent of other plastics of Polyolefin and; (6), improve the permeability resistance of other plastics of Polyolefin and as the barrier additive; (7) be used for tackiness agent or the like between polyolefine/other plastics, polyolefine/metal, polyolefine/paper and other material as hot melt adhesive.
Compare with the preparation method of existing nano composite polymer/laminated silicate material, the present invention has following characteristics:
(1) polyolefinic solid state grafting polymerization technology is combined with nanometer composite technology, promoted the nano combined of polymkeric substance and layered silicate;
(2) mixture of two or more monomer of employing (wherein at least a is polar monomer) in the solid phase grafting technology, on polyolefin backbone, connect and contain two or more monomeric multipolymer side chain, can obtain the graft copolymer of high percentage of grafting, long-chain branch, overcome usually with a kind of shortcoming that percentage of grafting is high, side chain is short when monomer-grafted such as maleic anhydride, not only help polyolefinic modification, and help promoting that polyolefine is compound at the intercalation nano of layered silicate interlayer;
(3) adopt the solid phase grafting technology, avoided use solvent and water, help environmental protection, equipment is simple, and is easy to operate, need not carry out aftertreatment to product after reaction finishes and can directly use, and significantly reduced the cost of nano composite material;
(4) product of the present invention is when keeping the polyolefine premium properties, intensity, modulus, toughness, polarity, wetting ability, reactivity and anti-small molecules perviousness etc. significantly improve and improve, can be used as the expanding material of polyolefine and polar polymer blend, the interface modifier of polyolefine and various filler and fortifying fibre also can be used as enhancing plasticized modifier, surface-modifying agent and the barrier additive etc. of other plastics of Polyolefin and.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
In taking back the special reactor of flow condenser, Powdered high density polyethylene(HDPE) (HDPE) resin 200 grams and organic quaternary ammonium salt modified polynite 100 are restrained uniform mixing, select for use maleic anhydride (MAH) 30 grams as first monomer, vinylbenzene (St) 70 grams are as second monomer, butyl acrylate (BA) 10 grams are the 3rd monomer, with dibenzoyl peroxide (BPO) 1.7 grams is initiator, add in the said mixture, be warming up to 110 ℃ of even stirring reactions 2 hours.Reaction product is through 60～80 ℃ of distilled water repetitive scrubbings, suction filtration, in baking oven under 80 ℃ of temperature dry 24 hours, promptly gets grafted polyethylene/laminated nm-silicate composite material (GPESNC) powder.Monomer is 10.4% to the percentage of grafting of HDPE in this material, and acid number is 10.5mgKOH/g.With this powder extruding pelletization on the small capacity double screw extrusion press of laboratory, promptly get the GPESNC pellet.
, add in the plastics such as polypropylene (PP), polyethylene (PE), nylon-6 as properties-correcting agent with above-mentioned GPESNC nano composite material, can obtain the nano composite material of excellent property.
Table 1,2,3 has been listed the physical and mechanical properties of the relevant nano composite material of GPESNC modification.As can be seen from the table, all obtain tangible raising with PP, the HDPE of a small amount of GPESNC (2～6 parts) modification, tensile strength, flexural strength, shock strength, initial heat decomposition temperature or the heat-drawn wire of PA-6 nano composite material.
The physical and mechanical properties of table 1GPESNC MODIFIED PP nano composite material
| GPESNC consumption (phr) | Tensile strength (MPa) | Flexural strength (MPa) | Shock strength (MPa) | Initial heat decomposition temperature (℃) |
| ????0 | ????34.0 | ????54.0 | ????3.7 | ????373.3 |
| ????2 | ????37.5 | ????79.5 | ????5.6 | ????- |
| ????4 | ????38.0 | ????88.0 | ????6.2 | ????423.8 |
| ????6 | ????38.0 | ????86.6 | ????6.4 | ????- |
| ????8 | ????38.2 | ????76.0 | ????5.8 | ????- |
| ????10 | ????38.0 | ????63.2 | ????5.1 | ????- |
The physical and mechanical properties of table 2GPESNC modification HDPE nano composite material
| GPESNC consumption (phr) | Tensile strength (MPa) | Flexural strength (MPa) | Shock strength (KJ/m 2) | Initial heat decomposition temperature (℃) |
| ????0 | ????22.0 | ????36.0 | ????9.0 | ????420.9 |
| ????2 | ????25.2 | ????51.0 | ????11.6 | ????- |
| ????4 | ????28.8 | ????62.6 | ????12.6 | ????436.5 |
| ????6 | ????27.5 | ????64.5 | ????11.7 | ????- |
| ????8 | ????26.3 | ????58.0 | ????11.5 | ????- |
| ????10 | ????25.5 | ????54.3 | ????10.8 | ????- |
The physical and mechanical properties of table 3GPESNC modification PA-6 nano composite material
Embodiment 2
| GPESNC consumption (phr) | Tensile strength (MPa) | Flexural strength (MPa) | Shock strength (KJ/m 2) | Heat-drawn wire (℃) |
| ????0 | ????75.0 | ????105.6 | ????12.0 | ????71.0 |
| ????2.5 | ????78.0 | ????154.0 | ????19.5 | ????78.0 |
In taking back the special reactor of flow condenser, the double bond containing organic modification montmonrillonite 300 of Powdered polypropylene (PP) resin 300 grams and interlayer surface is restrained uniform mixing, select for use maleic anhydride (MAH) 80 grams as first monomer, methyl methacrylate (MMA) 120 grams are as second monomer, butyl acrylate (BA) 30 grams are the 3rd monomer, with dibenzoyl peroxide (BPO) 3.5 grams is initiator, add in the said mixture, be warming up to 120 ℃ of even stirring reactions 1 hour.Reaction product is through 60～80 ℃ of deionized water repetitive scrubbings, suction filtration, in baking oven under 80 ℃ of temperature dry 24 hours, promptly gets graft polypropylene/laminated nm-silicate composite material powder (GPPSNC).Monomer is 13.1% to the percentage of grafting of PP in this powder, acid number 11.5mgKOH/g.This powder is promptly got the GPPSNC pellet with the twin screw extruder granulation.
In 100 parts of PP resins, add 10 parts of above-mentioned GPPSNC masterbatch, after injection moulding, measure its physical and mechanical properties and list in table 4.As can be seen, the performance through the composite nanometer-level polypropylene/montmorillonoid material of GPPSNC modification significantly improves than unmodified polypropylene.Table 5 has been listed the performance of polypropylene/nylon-6 (PP/PA-6) nano composite material of GPPSNC modification, demonstrates tangible enhancing toughening effect equally.
The performance of the composite nanometer-level polypropylene/montmorillonoid material of table 4GPPSNC modification
The performance of the polypropylene/nylon-6 nano composite material of table 5GPPSNC modification
Embodiment 3
| GPPSNC consumption (phr) | Tensile strength (MPa) | Flexural strength (MPa) | Modulus in flexure (Gpa) | Shock strength (KJ/m 2) |
| ????0 | ????29.3 | ????61.1 | ????1.5 | ????4.3 |
| ????3 | ????36.1 | ????88.3 | ????2.0 | ????7.5 |
| ????5 | ????39.6 | ????96.5 | ????2.6 | ????7.6 |
| ????7 | ????40.0 | ????115.6 | ????2.6 | ????7.5- |
| ????10 | ????39.2 | ????98.0 | ????2.5 | ????6.7- |
| GPPSNC consumption (phr) | Tensile strength (MPa) | Shock strength (KJ/m 2) |
| ????0 | ????24.6 | ????2.6 |
| ????4 | ????34.5 | ????3.8 |
| ????6 | ????35.0 | ????4.9 |
| ????10 | ????38.8 | ????5.0 |
In special reactor, Powdered new LDPE (film grade) (LDPE) resin 200 grams and organically-modified kaolin 150 are restrained uniform mixing, select for use maleic anhydride (MAH) 30 grams as first monomer, butyl acrylate (BA) 70 grams are as second monomer, with dibenzoyl peroxide (BPO) 1.5 gram and N, accelerine 1.5 grams are initiator, add in the said mixture, at the even stirring reaction 5 hours of room temperature (25 ℃).Reaction product is through 60～80 ℃ of distilled water repetitive scrubbings, suction filtration, in baking oven under 80 ℃ of temperature dry 24 hours, promptly gets grafting new LDPE (film grade)/laminated nm-silicate composite material (GLPESNC).Monomer is 9.8% to the percentage of grafting of LDPE in this material, acid number 8.3mgKOH/g.Promptly get GLPESNC matrix material pellet with the twin screw extruder granulation.
With tensile strength, flexural strength and the shock strength of the PP nano composite material of 8 parts of GLPESNC modifications never 34.0MPa, 54.0Mpa and the 3.7KJ/m of MODIFIED PP respectively
2Be increased to 36.4Mpa, 86.8Mpa and 8.5KJ/m
2, demonstrate significant enhancing toughening effect.
Embodiment 4
In special reactor, Powdered high density polyethylene(HDPE) (HDPE) resin 1000 grams and organic quaternary ammonium salt modified polynite 60 are restrained uniform mixing, select for use maleic anhydride (MAH) 90 grams as first monomer, methyl methacrylate (MMA) 210 grams are as second monomer, with Diisopropyl azodicarboxylate (AIBN) 6.0 grams is initiator, add in the said mixture, be warming up to 60 ℃ and evenly stir reaction down 8 hours.Reaction product is through 60～80 ℃ of deionized water repetitive scrubbings, suction filtration, in baking oven under 80 ℃ of temperature dry 24 hours, promptly gets grafted polyethylene/laminated nm-silicate composite material (GPESNC).Monomer is 6.5% to the percentage of grafting of HDPE in this material, acid number 3.6mgKOH/g.
Above-mentioned product mixtures is measured its physical and mechanical properties after twin screw extruder granulation and injection moulding machine moulding, its tensile strength, flexural strength, shock strength are respectively 28.0Mpa, 68.5Mpa and 13.8KJ/m
2, and the respective performances value of the unmodified HDPE of contrast is respectively 22.0Mpa, 36.0Mpa and 9.0KJ/m
2
Embodiment 5
In taking back the special reactor of flow condenser, the double bond containing organic modification montmonrillonite 240 of Powdered chlorinatedpolyethylene (CPE) 240 grams and interlayer surface is restrained uniform mixing, select for use vinylbenzene 120 grams as first monomer, vinyl cyanide 40 grams are as second monomer, dibenzoyl peroxide (BPO) 3.2 grams are initiator, add in the said mixture, be warming up to 95 ℃, evenly stirring reaction is 4 hours.Reaction product in 60 ℃ of baking ovens dry 24 hours promptly gets grafting chlorinatedpolyethylene/phyllosilicate nano composite master batch (GCPESNC).Monomer conversion is 90% in this masterbatch, percentage of grafting 15.0%.
8 parts of above-mentioned GCPESNC masterbatch are added in 100 parts of HDPE/AS (80/20) blend, the tensile strength of system is increased to 25.8Mpa by original 16.9Mpa, flexural strength is increased to 46.9Mpa by original 35.5Mpa, elongation at break is increased to 200% by original 3.5%, shows tangible modified effect.
Claims (6)
1, a kind of preparation method of graft polyolefin/lamellar silicate composite nanomaterial comprises the step of following order:
(1) in reactor, drops into a certain proportion of powdery polyolefin, organic modified sheet silicate, monomer mixture and initiator;
(2) stirring reaction under nitrogen protection, temperature is controlled at 20～150 ℃, and the reaction times is 0.5～5 hour;
(3) the reaction after product is through 60～80 ℃ of distilled water or deionized water repetitive scrubbing, and suction filtration under 50～90 ℃ of temperature dry 16～48 hours then, promptly gets the graft polyolefin/lamellar silicate composite nanomaterial powder;
(4) above-mentioned powder twin screw extruder granulation promptly obtains the graft polyolefin/lamellar silicate composite nanomaterial pellet.
2, the preparation method of a kind of graft polyolefin/lamellar silicate composite nanomaterial according to claim 1, it is characterized in that: the weight proportion of each raw material is 100 parts of polyolefine, 1～100 part of organic modified sheet silicate, mix monomer are 1～100 part, and initiator is 0.01～3.0 part.
3, the preparation method of a kind of graft polyolefin/lamellar silicate composite nanomaterial according to claim 1 is characterized in that: described polyolefine is polypropylene, high density polyethylene(HDPE), new LDPE (film grade), LLDPE or polyolefinic derivative.
4, the preparation method of a kind of graft polyolefin/lamellar silicate composite nanomaterial according to claim 1 is characterized in that: described organic modified sheet silicate is polynite, wilkinite, kaolin, potter's clay, talcum powder or mica powder with various organism intercalation modifyings.
5, the preparation method of a kind of graft polyolefin/lamellar silicate composite nanomaterial according to claim 1, it is characterized in that: described monomer mixture comprises two kinds of monomers at least, wherein must comprise at least a polar monomer, described monomer is maleic anhydride and ester, fumaric acid anhydride and ester thereof, vinylbenzene and derivative thereof, methacrylic acid and various methacrylic ester, vinylformic acid and various acrylate, vinyl cyanide, acrylamide, vinyl acetate, N-vinyl pyridine or long-chain unsaturated carboxylic acid.
6, the preparation method of a kind of graft polyolefin/lamellar silicate composite nanomaterial according to claim 1 is characterized in that: described initiator is peroxide initiator and redox system or azo-initiator.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326931C (en) * | 2004-12-12 | 2007-07-18 | 青岛大学 | Preparation method of polyolefin/layered silicate nano-composition |
| CN100350011C (en) * | 2005-12-28 | 2007-11-21 | 上海应用技术学院 | One-step preparation process of organic-montmorillonite modified ethylene-vinyl acetate hot-melt adhesive |
| CN100369971C (en) * | 2006-01-27 | 2008-02-20 | 华南理工大学 | Polyolefin/laminated silicate nanometer composite materials and production thereof |
| CN100478384C (en) * | 2005-02-22 | 2009-04-15 | 中国科学院化学研究所 | Functional polyolefin/montmorillonite nano-composite material and its preparation method |
| CN103044781A (en) * | 2013-01-23 | 2013-04-17 | 苏州润佳工程塑料股份有限公司 | High-modulus low-shrinkage low-filling polypropylene composite material |
| CN103059417A (en) * | 2013-01-23 | 2013-04-24 | 苏州润佳工程塑料股份有限公司 | Filled polypropylene composite material applied to rapid forming component |
| CN103360678A (en) * | 2012-03-30 | 2013-10-23 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene/montmorillonite/graphite nanocomposite material and preparation method for same |
| CN104151723A (en) * | 2014-08-12 | 2014-11-19 | 苏州卓越工程塑料有限公司 | Filled polybutylene composite material used in fast-forming parts, and preparation method thereof |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
| CN106221106A (en) * | 2016-08-05 | 2016-12-14 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of rubber tyre carcass resisting fatigue auxiliary agent |
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2002
- 2002-08-27 CN CNB02134616XA patent/CN1176962C/en not_active Expired - Fee Related
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| CN1326931C (en) * | 2004-12-12 | 2007-07-18 | 青岛大学 | Preparation method of polyolefin/layered silicate nano-composition |
| CN100478384C (en) * | 2005-02-22 | 2009-04-15 | 中国科学院化学研究所 | Functional polyolefin/montmorillonite nano-composite material and its preparation method |
| CN100350011C (en) * | 2005-12-28 | 2007-11-21 | 上海应用技术学院 | One-step preparation process of organic-montmorillonite modified ethylene-vinyl acetate hot-melt adhesive |
| CN100369971C (en) * | 2006-01-27 | 2008-02-20 | 华南理工大学 | Polyolefin/laminated silicate nanometer composite materials and production thereof |
| CN103360678A (en) * | 2012-03-30 | 2013-10-23 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene/montmorillonite/graphite nanocomposite material and preparation method for same |
| CN103059417A (en) * | 2013-01-23 | 2013-04-24 | 苏州润佳工程塑料股份有限公司 | Filled polypropylene composite material applied to rapid forming component |
| CN103044781A (en) * | 2013-01-23 | 2013-04-17 | 苏州润佳工程塑料股份有限公司 | High-modulus low-shrinkage low-filling polypropylene composite material |
| CN104151723A (en) * | 2014-08-12 | 2014-11-19 | 苏州卓越工程塑料有限公司 | Filled polybutylene composite material used in fast-forming parts, and preparation method thereof |
| CN104744842A (en) * | 2015-03-24 | 2015-07-01 | 合肥会通新材料有限公司 | Polystyrene composite material reinforced by in situ-polymerization of montmorillonite intercalation and preparation method of polystyrene composite material |
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| CN107459655A (en) * | 2017-08-17 | 2017-12-12 | 美巢集团股份公司 | A kind of environmentally friendly low VOC interface treating agents and preparation method thereof |
| CN107459655B (en) * | 2017-08-17 | 2020-09-08 | 美巢集团股份公司 | Environment-friendly low-VOC interface treating agent and preparation method thereof |
| CN108164752A (en) * | 2018-01-26 | 2018-06-15 | 刘成旭 | The PVC cable material fire retardant prepared based on nano combined intercalation technique |
| CN108285284A (en) * | 2018-01-26 | 2018-07-17 | 淮南市晋淮建化科技有限公司 | A kind of super hardening water-reducing agent for hydraulic engineering and salvaging |
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