CN103483504A - Method for preparing polycarboxylate superplasticizer by combination of polyether macromonomers of two structures - Google Patents
Method for preparing polycarboxylate superplasticizer by combination of polyether macromonomers of two structures Download PDFInfo
- Publication number
- CN103483504A CN103483504A CN201310416209.1A CN201310416209A CN103483504A CN 103483504 A CN103483504 A CN 103483504A CN 201310416209 A CN201310416209 A CN 201310416209A CN 103483504 A CN103483504 A CN 103483504A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- monomers
- reducer
- molecular weight
- polycarboxylate water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention discloses a method for preparing polycarboxylate superplasticizer by the combination of polyether macromonomers of two structures. The method is characterized by comprising the steps that a macromonomer A (methyl allyl polyoxyethylene ether), a macromonomer C (methyl-2-buten-1-ol polyoxyethylene ether) and water are added into a reactor and are stirred, mixed and dissolved at 40-60 DEG C, then small monomers (acrylic acid and the like) are added, mercaptoacetic acid is added, the temperature is increased to be 75-85 DEG C, an ammonium persulfate solution is added dropwise within 70-90min, heat preservation is carried out for 2-3 hours at the 75-85 DEG C to perform polymerization reaction, then materials after reaction are cooled to be at the room temperature, and the materials are neutralized through a sodium hydroxide aqueous solution of the mass percent concentration being 30% until the pH value ranges from 6.8 to 7.2 so as to prepare the polycarboxylate superplasticizer. The macromonomers and the like are combined and copolymerized, the polycarboxylate superplasticizer with high performance is compounded, and balance and performance regulation between slushing and slump retaining of existing polycarboxylate superplasticizer products are facilitated.
Description
Technical field
The invention belongs to the preparation for the macromolecular compound of concrete or resemble construction material, the large combination of monomers of polyethers that relates to two kinds of structures prepares the method for polycarboxylate water-reducer.The polycarboxylate water-reducer of preparation is applicable makes the composition material of concrete etc., to construct the concrete structure of (large span) bridge, (high level) building etc.
Background technology
Concrete is the material of construction of usage quantity maximum in the world today, and the development of concrete admixture is remarkable to the effect of modern concrete, is the key strength that promotes the concrete technology progress.At present concrete enters " green ", " high-performance " epoch, and correspondingly to concrete starting material, workability, weather resistance, energy-conserving and environment-protective, and economy etc. is had higher requirement.Polycarboxylate water-reducer has low-dosage, high water reducing rate, low chlorine, low alkali, low slump loss, clean environment firendly, and characteristics such as cement adaptability preferably, has become the focus of current concrete admixture area research and application.From naphthalene system, melamine series, amido sulfoacid series and fatty family etc., adopt the synthetic high efficiency water reducing agent of formaldehyde condensation polymer different, what polycarboxylate water-reducer adopted is that Raolical polymerizable is synthetic, and the molecular structure designability is strong, the capable of regulating space is large.Polycarboxylate water-reducer is comb shaped structure, main chain is generally fatty segment, and containing long side chain and several functions group (as hydroxyl, carboxyl, sulfonic group, ester group, ether, itrile group, amide group, imide, and siloxy etc.), thereby give its rich and varied performance variation; The molecular weight of density degree in the water reducer molecule of function base kind and quantity, long side-chain structure and molecular weight, long side group, water reducer and molecular weight distribution etc. all can affect the performance of polycarboxylate water-reducer greatly.The current infrastructure construction peak period that is in of China, cement and concrete amount are huge, approach 60% of world's total amount, thereby, to the demand of concrete admixture, the demand that especially has the polycarboxylate water-reducer of excellent properties is very huge.
With regard to polycarboxylate water-reducer overall development level, China compared with developed countries, also has larger gap, particularly in kind, functional, otherness, and the aspect Shortcomings such as water reducer Molecular Structure Design, of less types, the large monomer functional base of the critical materials surface-active macromonomer of synthetic polycarboxylate water-reducer is single etc., causes domestic polycarboxylate water-reducer product homogeneity.Therefore, research and utilization existing business sell surface-active macromonomer, the different sorts of research surface-active macromonomer, the combination between different varieties, and the synthesizing new polycarboxylate water-reducer is very necessary.
In prior art, mostly adopt the minor comonomer copolymerizations such as the large monomer of ethers and vinylformic acid, maleic anhydride during polycarboxylate water-reducer is synthetic, the large monomer of ethers used is all congener single large monomer, thereby the aspect of performance of the water reducer of synthesized has certain limitation, be difficult to meet actual needs.
Summary of the invention
Purpose of the present invention is intended to overcome deficiency of the prior art, provides the large combination of monomers of polyethers of two kinds of structures to prepare the method for polycarboxylate water-reducer.The present invention adopts the large monomer mixing of ethers not of the same race copolymerization, the large monomer mixing copolymerization, the chain structure that are about to methacrylic Soxylat A 25-7 and two kinds of different activities of prenol Soxylat A 25-7 complement one another, thereby provide a kind of large combination of monomers of polyethers that can effectively improve two kinds of structures of polycarboxylate water-reducer over-all properties, excellent property to prepare the method for polycarboxylate water-reducer.
Content of the present invention is: the large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, it is characterized in that comprising the following steps: by large monomer A 5～30 mass parts, large monomer C6.8～46.6 mass parts, and water 40～65 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 0.2～1.2 mass parts, be warming up to 75 ℃～85 ℃, ammonium persulphate (as the initiator) aqueous solution 15～30 mass parts that to be added dropwise to mass percent concentration within the time of 70min～90min be 2.4～3.0%, be incubated 2～3h again at the temperature of 75 ℃～85 ℃ and carry out polyreaction, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer,
Described large monomer A is methacrylic Soxylat A 25-7 (being called for short HPEG, 4C), and the chemical structural formula of this large monomer A is as follows:
In formula: n=32～44, the average molecular weight range of large monomer A is 1500～2000; For n=39, molecular weight, be 1788 preferably;
Described large monomer C is prenol Soxylat A 25-7 (being called for short TPEG, 5C), and the chemical structural formula of this large monomer C is as follows:
In formula: m=52～62, the average molecular weight range of large monomer C is 2400～2814; For m=62, molecular weight, be 2814 preferably;
Described minor comonomer is vinylformic acid 3.5～20 mass parts (being preferably 4～20 mass parts).
In content of the present invention: described large monomer A 5～30 mass parts, large monomer C6.8～46.6 mass parts can replace with large monomer A 6.0～35.2 mass parts, large monomers B 9.2～54.8 mass parts;
Described large monomers B is prenol Soxylat A 25-7 (being called for short TPEG, 5C), and the chemical structural formula of this large monomers B is as follows:
M=32 in formula～44, the average molecular weight range of large monomers B is 1500～2000; For m=36, molecular weight, be 1670 preferably.
In content of the present invention: described minor comonomer is that can to replace with described minor comonomer be vinylformic acid 3.5～12 mass parts and sodium allylsulfonate 0.05～2 mass parts to vinylformic acid 3.5～12 mass parts.
In content of the present invention: described minor comonomer is that can also to replace with described minor comonomer be vinylformic acid 3.5～12 mass parts, sodium allylsulfonate 0.05～2 mass parts and vinyl cyanide 0.05～1.00 mass parts to vinylformic acid 3.5～12 mass parts.
In foregoing: be 1788 for n=39, molecular weight preferably in the chemical structural formula of described large monomer A; In the chemical structural formula of described large monomer C, for m=62, molecular weight, be 2814 preferably.
In foregoing: be 1670 for m=36, molecular weight preferably in the chemical structural formula of described large monomers B.
Building-up reactions principle of the present invention is: by ternary, quaternary, the proportioning mode of five yuan, under the initiator condition, each monomer carries out radical polymerization in the aqueous solution.
The reaction formula of binary polymerization is as follows:
The reaction formula of four-element polymerization is as follows:
The reaction formula of five yuan of polymerizations is as follows:
In above-mentioned reaction formula: described binary polymerization is that large monomer is A and B or A and two kinds of large monomers of C and the acrylic acid terpolymer of minor comonomer; Described four-element polymerization is that large monomer is the quarternary copolymerized of A and B or A and two kinds of large monomers of C and vinylformic acid and two kinds of minor comonomers of sodium allylsulfonate; Described five yuan of polymerizations are that large monomer is A and B or A and two kinds of large monomers of C, and vinylformic acid, sodium allylsulfonate and three kinds of minor comonomers of vinyl cyanide is penta-component copolymerized.
Sign and the physical property measurement of the polycarboxylate water-reducer of preparation: the polycarboxylate water-reducer to preparation adopts infrared analysis (FT-IR) and gel permeation chromatography (GPC) to carry out structural characterization; Adopt cement paste test and concrete test to carry out performance evaluation.
In content of the present invention: described surface-active macromonomer molecular structure by
1h-NMR characterizes; Molecular weight by
1h-NMR calculation result and GPC measurement result obtain.Warp
1h-NMR characterizes, and can determine that large monomer A is methacrylic Soxylat A 25-7 (HPEG, 4C), and large monomers B and C are prenol Soxylat A 25-7 (TPEG, 5C).
In content of the present invention: through infrared spectra and gel permeation chromatography, characterize (the analytical data of infrared and GPC, see the accompanying drawing explanation), in the polycarboxylate water-reducer that polymkeric substance of synthesized makes, the characteristic group has appearred, the polycarboxylate water-reducer polymer average molecular weight made is between 40000～100000, and the polycarboxylate water-reducer molecule has higher dispersive ability in this scope.
In content of the present invention: in the performance test of the polycarboxylate water-reducer made, the flowing degree of net paste of cement experiment is tested according to GB GB/T8077-2000 " concrete admixture uniformity test method "; Concrete test is according to GB GB/T50080-2002 " normal concrete mix performance test standard "; GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete " carries out correlation test.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention adopts the mode of the large combination of monomers of different molecular structures, through the synthetic polycarboxylate water-reducer of multiple aggregation (being called for short PC), advantage in conjunction with two kinds of different structures (structure, molecular weight) large monomer of polyethers, synthetic molecules is rational in infrastructure, molecular weight is moderate, can effectively improve the polycarboxylate water-reducer over-all properties, functional;
(2) adopt the present invention, the synthetic polycarboxylate water-reducer made, in the situation that the solid volume of folding is 0.10%, initial clean slurry degree of mobilization reaches 270～320mm; When the solid volume of this water reducer folding is 0.15%, the concrete mix slump can reach 200mm ± 20mm, the slump-loss of 1h is in 10mm, and water-reducing rate can reach more than 25%, and 3d, 7d, 28d compressive strength rate are respectively 125%～135%, 140%～155%, 130%～150%; Surface-active macromonomer by two kinds of structures is used in combination, with prior art products, compare, the present invention affects the structure of polycarboxylate water-reducer (as chain flexibility by the textural difference of surface-active macromonomer, and the inertia of side group intercepts and sterically hindered etc.) and the performance (adsorptivity of cement particle polycarboxylate water-reducer, and polycarboxylate water-reducer to the dispersiveness of cement and disperse hold facility etc.), play the effects such as relation between the water-reducing rate of balance polycarboxylate water-reducer better and function of slump protection etc.; The polycarboxylate water-reducer prepared by the present invention, when the condition than low-dosage, has higher water-reducing rate, and has excellent dispersion retentivity and the growth of each age concrete ultimate compression strength concurrently;
(3) the present invention adopts large monomer etc. to be combined copolymerization, the polycarboxylate water-reducer of synthesized high-performance, balance and performance adjustment between the diminishing that is conducive to existing polycarboxylate water-reducer product collapses with the guarantor; Preparation technology is simple, and operation is easy, easily-controlled reaction conditions, and processing ease, practical.
The accompanying drawing explanation
Fig. 1 is the infrared spectrogram (FT-IR) of the polycarboxylate water-reducer for preparing of the terpolymer for preparing in the embodiment of the present invention, and in Fig. 1, X-coordinate is wave number (cm
-1), ordinate zou is transmitance (%); In infrared spectrum, 1730.9cm
-1for carboxylic acid carbonyl C=O shrinks vibration peak; 529.3cm
-1in-plane bending vibration peak for carboxylic acid C-C=O; 1114.1cm
-1stretching vibration peak for C-O-C in large monomer ether; Above characteristic peak can show vinylformic acid and the copolymerization in solution of the large monomer of two class polyethers, has generated polycarboxylate water-reducer;
Fig. 2 is the gel permeation chromatography (GPC) of the quarternary copolymerized polycarboxylate water-reducer for preparing in the embodiment of the present invention; From last measurement result, Mw=4.46 * 10
4, Mn=4.13 * 10
4, Mw/Mn=1.08, molecular-weight average is moderate, and molecular weight distribution is narrower; Moderate molecular weight explanation copolymer chain ankylose reason is comparatively favourable to water-reducing rate; The narrower explanation water reducer of molecular weight distribution structure is comparatively even.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that the person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, under 50 ℃ of conditions, by the large monomer A of 11.0g, 17.1g large monomer C and 55g water add in flask, flask are put into to the oil bath of magnetic stirring apparatus, heated and stirred under 40 ℃～50 ℃ conditions, after fully dissolving, add again 4g vinylformic acid, and the 0.4g Thiovanic acid, be warming up to 80 ℃ after stirring.Splash into the ammonium persulfate solution 15g that mass concentration is 2.6% by a dropping funnel in flask.After dropwising, at this temperature, insulation is 2 hours, then is cooled to 30 ℃, then adds NaOH solution that mass concentration is 30% to regulate the PH to 7.0 of gained solution, obtains polycarboxylate water-reducer.
Embodiment 2:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, under 50 ℃ of conditions, by the large monomer A of 11.0g, 17.1g large monomer C and 55g water add in flask, flask are put into to the oil bath of magnetic stirring apparatus, heated and stirred under 40 ℃～50 ℃ conditions, after fully dissolving, add 4g vinylformic acid, 0.08g sodium allylsulfonate and 0.4g Thiovanic acid, be warming up to 78 ℃ after stirring again.Splash into the ammonium persulfate solution 15g that mass concentration is 3.0% by a dropping funnel in flask.After dropwising, at this temperature, insulation is 2 hours, then is cooled to 30 ℃, then adds NaOH solution that mass concentration is 30% to regulate the PH to 7.2 of gained solution, obtains polycarboxylate water-reducer.
Embodiment 3:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, under 50 ℃ of conditions, by the large monomer A of 8.82g, the large monomers B of 13.72g and 55g water add in flask, flask are put into to the oil bath of magnetic stirring apparatus, heated and stirred under 40 ℃～50 ℃ conditions, after fully dissolving, then add 3.98g vinylformic acid, the 0.1g sodium allylsulfonate, 0.06g vinyl cyanide and 0.4g Thiovanic acid, be warming up to 85 ℃ after stirring.Splash into the ammonium persulfate solution 15g that mass concentration is 2.6% by a dropping funnel in flask.After dropwising, at this temperature, insulation is 2 hours, then is cooled to 30 ℃, then adds NaOH solution that mass concentration is 30% to regulate the PH to 6.8 of gained solution, obtains polycarboxylate water-reducer.
Embodiment 4:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, under 50 ℃ of conditions, by the large monomer A of 11.0g, 20.7g large monomers B and 55g water add in flask, flask is put into to the oil bath of magnetic stirring apparatus, heated and stirred under 40 ℃～50 ℃ conditions, after fully dissolving, add again 4g vinylformic acid and 0.4g Thiovanic acid, be warming up to 75 ℃ after stirring.Splash into the ammonium persulfate solution 15g that mass concentration is 2.6% by a dropping funnel in flask.After dropwising, at this temperature, insulation is 2 hours, then is cooled to 30 ℃, then adds NaOH solution that mass concentration is 30% to regulate the PH to 7.2 of gained solution, obtains polycarboxylate water-reducer.
Embodiment 5:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, under 50 ℃ of conditions, by the large monomer A of 11.0g, 20.7g large monomer C and 55g water add in flask, flask are put into to the oil bath of magnetic stirring apparatus, heated and stirred under 40 ℃～50 ℃ conditions, after fully dissolving, add 4g vinylformic acid, 0.08g sodium allylsulfonate and 0.4g Thiovanic acid, be warming up to 75 ℃ after stirring again.Splash into the ammonium persulfate solution 15g that mass concentration is 2.6% by a dropping funnel in flask.After dropwising, at this temperature, insulation is 2 hours, then is cooled to 30 ℃, then adds NaOH solution that mass concentration is 30% to regulate the PH to 7.0 of gained solution, obtains polycarboxylate water-reducer.
Application Example:
Synthetic polycarboxylate water-reducer is carried out to cement paste experiment, concrete test.The performance index of polycarboxylate water-reducer are according to industry standard JG/T223-2007 " polycarboxylate high performance water-reducing agent "; The flowing degree of net paste of cement experiment is tested according to GB GB/T8077-2000 " concrete admixture uniformity test method ", and the solid volume of water reducer folding is 0.1%, and test result is shown in Table 1; Concrete test is according to GB GB/T50080-2002 " normal concrete mix performance test standard ", and the solid volume of water reducer folding is 0.15%; GB-T50081-2002 " standard for test methods of mechanical properties of ordinary concrete " carries out correlation test.
Table 1: application performance test result:
Illustrate: the solid volume 0.10% of polycarboxylate water-reducer folding, middle P.O42.5R cement (connection Cement Co., Ltd production in China's associating Cement Group Beichuan).
Table 2:C
30the concrete test result:
Illustrate: the solid volume 0.15% of test polycarboxylate water-reducer folding, adopt metal working P.O42.5R cement (production of Sichuan metal working Cement Co., Ltd), medium sand (Machine-made Sand), 5～25 continuous size fraction rubbles, every side's consumption 360 ㎏ of cement, sand coarse aggregate ratio is 45%.
Embodiment 6:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 5～30 mass parts, large monomer C6.8～46.6 mass parts, and water 40～65 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 0.2～1.2 mass parts, be warming up to 75 ℃～85 ℃, ammonium persulphate (as the initiator) aqueous solution 15～30 mass parts that to be added dropwise to mass percent concentration within the time of 70min～90min be 2.4～3.0%, be incubated 2～3h again at the temperature of 75 ℃～85 ℃ and carry out polyreaction, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer,
Described large monomer A is methacrylic Soxylat A 25-7 (being called for short HPEG, 4C), and the chemical structural formula of this large monomer A is as follows:
In formula: n=32～44, the average molecular weight range of large monomer A is 1500～2000; For n=39, molecular weight, be 1788 preferably;
Described large monomer C is prenol Soxylat A 25-7 (being called for short TPEG, 5C), and the chemical structural formula of this large monomer C is as follows:
In formula: m=52～62, the average molecular weight range of large monomer C is 2400～2814; For m=62, molecular weight, be 2814 preferably;
Described minor comonomer is vinylformic acid 3.5～20 mass parts (being preferably 4～20 mass parts).
Embodiment 7:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 5 mass parts, large monomer C6.8 mass parts, and water 40 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 0.2 mass parts, be warming up to 75 ℃～85 ℃, ammonium persulphate (as the initiator) aqueous solution 15 mass parts that to be added dropwise to mass percent concentration within the time of 70min be 2.4%, at the temperature of 75 ℃～85 ℃, insulation 2h carries out polyreaction again, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer, described minor comonomer is vinylformic acid 3.5 mass parts, other omits with embodiment 6.
Embodiment 8:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 30 mass parts, large monomer C46.6 mass parts, and water 65 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 1.2 mass parts, be warming up to 75 ℃～85 ℃, ammonium persulphate (as the initiator) aqueous solution 30 mass parts that to be added dropwise to mass percent concentration within the time of 90min be 3.0%, at the temperature of 75 ℃～85 ℃, insulation 3h carries out polyreaction again, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer, described minor comonomer is vinylformic acid 20 mass parts, other omits with embodiment 6.
Embodiment 9:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 18 mass parts, large monomer C26 mass parts, and water 52 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 0.7 mass parts, be warming up to 75 ℃～85 ℃, ammonium persulphate (as the initiator) aqueous solution 22 mass parts that to be added dropwise to mass percent concentration within the time of 80min be 2.7%, at the temperature of 75 ℃～85 ℃, insulation 2.5h carries out polyreaction again, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer, described minor comonomer is vinylformic acid 12 mass parts, other omits with embodiment 6.
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 5～30 mass parts, large monomer C6.8～46.6 mass parts, and water 40～65 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 0.2～1.2 mass parts, be warming up to 75 ℃～85 ℃, ammonium persulphate (as the initiator) aqueous solution 15～30 mass parts that to be added dropwise to mass percent concentration within the time of 70min～90min be 2.6%, at the temperature of 75 ℃～85 ℃, insulation 2.5h carries out polyreaction again, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer, described minor comonomer is vinylformic acid 3.5～20 mass parts, other omits with embodiment 6,
In each embodiment, the concrete mass parts consumption of each feed composition sees the following form 3:
Table 3:
Embodiment 17～23:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, and large monomer A 5～30 mass parts described in embodiment 6, large monomer C6.8～46.6 mass parts are replaced with to large monomer A 6.0～35.2 mass parts, large monomers B 9.2～54.8 mass parts;
In each embodiment, the concrete mass parts consumption of each feed composition can see the following form 4:
Table 4:
Described large monomers B is prenol Soxylat A 25-7 (being called for short TPEG, 5C), and the chemical structural formula of this large monomers B is as follows:
M=32 in formula～44, the average molecular weight range of large monomers B is 1500～2000; For m=36, molecular weight, be 1670 preferably;
Other omits with arbitrary in embodiment 6～16.
Embodiment 24:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 6.0 mass parts, large monomers B 9.2 mass parts, and water 40 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 0.2 mass parts, be warming up to 75 ℃, ammonium persulphate (as the initiator) aqueous solution 15 mass parts that to be added dropwise to mass percent concentration within the time of 70min be 2.4%, at the temperature of 75 ℃, insulation 3h carries out polyreaction again, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer,
Described large monomer A is methacrylic Soxylat A 25-7 (being called for short HPEG, 4C), and the chemical structural formula of this large monomer A is as follows:
In formula: n=32～44, the average molecular weight range of large monomer A is 1500～2000; For n=39, molecular weight, be 1788 preferably;
Described large monomers B is prenol Soxylat A 25-7 (being called for short TPEG, 5C), and the chemical structural formula of this large monomers B is as follows:
M=32 in formula～44, the average molecular weight range of large monomers B is 1500～2000; For m=36, molecular weight, be 1670 preferably;
Described minor comonomer is vinylformic acid 3.5 mass parts.
Embodiment 25:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 35.2 mass parts, large monomers B 54.8 mass parts, and water 65 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 1.2 mass parts, be warming up to 85 ℃, ammonium persulphate (as the initiator) aqueous solution 30 mass parts that to be added dropwise to mass percent concentration within the time of 90min be 3.0%, at the temperature of 85 ℃, insulation 2h carries out polyreaction again, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer,
Described large monomer A is methacrylic Soxylat A 25-7 (being called for short HPEG, 4C), and the chemical structural formula of this large monomer A is as follows:
In formula: n=32～44, the average molecular weight range of large monomer A is 1500～2000; For n=39, molecular weight, be 1788 preferably;
Described large monomers B is prenol Soxylat A 25-7 (being called for short TPEG, 5C), and the chemical structural formula of this large monomers B is as follows:
M=32 in formula～44, the average molecular weight range of large monomers B is 1500～2000; For m=36, molecular weight, be 1670 preferably;
Described minor comonomer is vinylformic acid 20 mass parts.
Embodiment 26:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, comprise the following steps: large monomer A 20 mass parts, large monomers B 32 mass parts, and water 53 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ (being preferably 40 ℃～50 ℃) after, add again minor comonomer, add Thiovanic acid (as chain-transfer agent) 0.6 mass parts, be warming up to 80 ℃, ammonium persulphate (as the initiator) aqueous solution 20 mass parts that to be added dropwise to mass percent concentration within the time of 80min be 2.8%, at the temperature of 80 ℃, insulation 2.5h carries out polyreaction again, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer,
Described large monomer A is methacrylic Soxylat A 25-7 (being called for short HPEG, 4C), and the chemical structural formula of this large monomer A is as follows:
In formula: n=32～44, the average molecular weight range of large monomer A is 1500～2000; For n=39, molecular weight, be 1788 preferably;
Described large monomers B is prenol Soxylat A 25-7 (being called for short TPEG, 5C), and the chemical structural formula of this large monomers B is as follows:
M=32 in formula～44, the average molecular weight range of large monomers B is 1500～2000; For m=36, molecular weight, be 1670 preferably;
Described minor comonomer is vinylformic acid 12 mass parts.
Embodiment 27～33:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, by minor comonomer described in above-described embodiment, is that to replace with described minor comonomer be vinylformic acid 3.5～12 mass parts and sodium allylsulfonate 0.05～2 mass parts for vinylformic acid and mass parts thereof;
In each embodiment, the concrete mass parts consumption of each feed composition can see the following form 5:
Table 5:
Other omits with arbitrary in embodiment 6～26.
Embodiment 34～40:
The large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, it is characterized in that: by minor comonomer described in above-described embodiment, be that to replace with described minor comonomer be vinylformic acid 3.5～12 mass parts, sodium allylsulfonate 0.05～2 mass parts and vinyl cyanide 0.05～1.00 mass parts for vinylformic acid and mass parts thereof;
In each embodiment, the concrete mass parts consumption of each feed composition can see the following form 6:
Table 6:
Other omits with arbitrary in embodiment 6～26.
In above-described embodiment: be 1788 for n=39, molecular weight preferably in the chemical structural formula of described large monomer A; In the chemical structural formula of described large monomer C, for m=62, molecular weight, be 2814 preferably.
In above-described embodiment: be 1670 for m=36, molecular weight preferably in the chemical structural formula of described large monomers B.
In above-described embodiment: each raw material adopted is commercially available prod.
In above-described embodiment: in the percentage adopted, do not indicate especially, be quality (weight) percentage or well known to a person skilled in the art percentage; Described quality (weight) part can be all gram or kilogram.
In above-described embodiment: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
In content of the present invention and above-described embodiment, the not concrete technology contents of narrating is with existing technology.
The invention is not restricted to above-described embodiment, content of the present invention is described all can implement and have described good result.
Claims (10)
1. the large combination of monomers of the polyethers of two kinds of structures prepares the method for polycarboxylate water-reducer, it is characterized in that comprising the following steps: by large monomer A 5～30 mass parts, large monomer C6.8～46.6 mass parts, and water 40～65 mass parts join in reactor, be uniformly mixed dissolving at the temperature of 40 ℃～60 ℃ after, add again minor comonomer, add Thiovanic acid 0.2～1.2 mass parts, be warming up to 75 ℃～85 ℃, ammonium persulfate aqueous solution 15～30 mass parts that to be added dropwise to mass percent concentration within the time of 70min～90min be 2.4～3.0%, be incubated 2～3h again at the temperature of 75 ℃～85 ℃ and carry out polyreaction, then reacting rear material is cooled to room temperature, the aqueous sodium hydroxide solution that is 30% with mass percent concentration is neutralized to pH=6.8～7.2, make polycarboxylate water-reducer,
Described large monomer A is the methacrylic Soxylat A 25-7, and the chemical structural formula of this large monomer A is as follows:
In formula: n=32～44, the average molecular weight range of large monomer A is 1500～2000;
Described large monomer C is the prenol Soxylat A 25-7, and the chemical structural formula of this large monomer C is as follows:
In formula: m=52～62, the average molecular weight range of large monomer C is 2400～2814;
Described minor comonomer is vinylformic acid 3.5～20 mass parts.
2. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 1, it is characterized in that: described large monomer A 5～30 mass parts, large monomer C6.8～46.6 mass parts replace with large monomer A 6.0～35.2 mass parts, large monomers B 9.2～54.8 mass parts;
Described large monomers B is the prenol Soxylat A 25-7, and the chemical structural formula of this large monomers B is as follows:
M=32 in formula～44, the average molecular weight range of large monomers B is 1500～2000.
3. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 1 or 2, it is characterized in that: described minor comonomer is that to replace with described minor comonomer be vinylformic acid 3.5～12 mass parts and sodium allylsulfonate 0.05～2 mass parts to vinylformic acid 3.5～12 mass parts.
4. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 1 or 2, it is characterized in that: described minor comonomer is that to replace with described minor comonomer be vinylformic acid 3.5～12 mass parts, sodium allylsulfonate 0.05～2 mass parts and vinyl cyanide 0.05～1.00 mass parts to vinylformic acid 3.5～12 mass parts.
5. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 1 or 2, it is characterized in that: be 1788 for n=39, molecular weight preferably in the chemical structural formula of described large monomer A; In the chemical structural formula of described large monomer C, for m=62, molecular weight, be 2814 preferably.
6. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 3, it is characterized in that: be 1788 for n=39, molecular weight preferably in the chemical structural formula of described large monomer A; In the chemical structural formula of described large monomer C, for m=62, molecular weight, be 2814 preferably.
7. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 4, it is characterized in that: be 1788 for n=39, molecular weight preferably in the chemical structural formula of described large monomer A; In the chemical structural formula of described large monomer C, for m=62, molecular weight, be 2814 preferably.
8. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of claim 2,6 or 7 described two kinds of structures, it is characterized in that: be 1670 for m=36, molecular weight preferably in the chemical structural formula of described large monomers B.
9. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 3, it is characterized in that: be 1670 for m=36, molecular weight preferably in the chemical structural formula of described large monomers B.
10. prepare the method for polycarboxylate water-reducer by the large combination of monomers of polyethers of the described two kinds of structures of claim 4, it is characterized in that: be 1670 for m=36, molecular weight preferably in the chemical structural formula of described large monomers B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310416209.1A CN103483504B (en) | 2013-09-12 | 2013-09-12 | The method of polycarboxylate water-reducer is prepared in the polyether macromonomer combination of two kinds of structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310416209.1A CN103483504B (en) | 2013-09-12 | 2013-09-12 | The method of polycarboxylate water-reducer is prepared in the polyether macromonomer combination of two kinds of structures |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103483504A true CN103483504A (en) | 2014-01-01 |
| CN103483504B CN103483504B (en) | 2016-04-06 |
Family
ID=49824135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310416209.1A Active CN103483504B (en) | 2013-09-12 | 2013-09-12 | The method of polycarboxylate water-reducer is prepared in the polyether macromonomer combination of two kinds of structures |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103483504B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177558A (en) * | 2014-08-26 | 2014-12-03 | 山东宏艺科技股份有限公司 | polycarboxylate-type water-reducer and preparation method thereof |
| CN104692699A (en) * | 2015-02-05 | 2015-06-10 | 石家庄市长安育才建材有限公司 | Early strength type ether polycarboxylate superplasticizer and preparation method thereof |
| CN104710310A (en) * | 2015-01-23 | 2015-06-17 | 四川同舟化工科技有限公司 | O-maleoyl lactate compound, preparation method thereof, and application of compound in synthesis of polycarboxylic superplasticizers |
| CN105801773A (en) * | 2014-12-29 | 2016-07-27 | 辽宁奥克化学股份有限公司 | Comb-type polymer and its preparation method and use as water reducer |
| US9453097B2 (en) | 2015-02-15 | 2016-09-27 | Beijing University Of Technology | Method for preparation of polycarboxylate superplasticizer by graft copolymerization of fatty acid vinyl ester onto acrylate polymer |
| CN106008849A (en) * | 2016-05-26 | 2016-10-12 | 四川恒泽建材有限公司 | Water reducing agent polymerized from polyethenoxy ethers with different molecular weights and preparation method thereof |
| CN106478891A (en) * | 2016-10-27 | 2017-03-08 | 湖南大学 | A kind of polyurethane-modified high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof |
| CN106632881A (en) * | 2016-09-29 | 2017-05-10 | 湖北工业大学 | Low water-reducing and high slump loss resistant type polycarboxylate superplasticizer master batch |
| CN106893047A (en) * | 2017-02-08 | 2017-06-27 | 山东卓星化工有限公司 | The method that solid polycarboxylic acid water reducing agent is prepared using organic oxidation reduction system |
| CN108329471A (en) * | 2017-01-19 | 2018-07-27 | 天津大学 | A kind of lithium-sulphur cell positive electrode active material prenol-sulphur copolymer and preparation method |
| CN110003405A (en) * | 2019-04-24 | 2019-07-12 | 四川同舟化工科技有限公司 | Comprehensive high-performance polycarboxylic acids diminishing |
| WO2022194996A1 (en) | 2021-03-17 | 2022-09-22 | Sika Technology Ag | Copolymers useful to retain high slump flow of mineral binder composition, their production and use |
| EP4306495A1 (en) | 2022-07-12 | 2024-01-17 | Sika Technology AG | Copolymers of carboxylates and polyethers comprising polyether side chains of different length, and use thereof in mineral binder compositions |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1655272A1 (en) * | 2004-11-04 | 2006-05-10 | Mapei S.p.A. | Superplasticizers for extending the workability of mortars |
| CN101735411A (en) * | 2010-01-08 | 2010-06-16 | 北京工业大学 | Method for preparing sustained-release polycarboxylic water reducer |
| CN101913793A (en) * | 2010-08-19 | 2010-12-15 | 上海三瑞高分子材料有限公司 | Polyocarboxylic acid high-performance water reducer |
| CN102491678A (en) * | 2011-11-28 | 2012-06-13 | 新疆西建新材料科技有限公司 | Modified polycarboxylic high performance water reducer and its production method and application method |
| CN102515616A (en) * | 2011-11-24 | 2012-06-27 | 上海大学 | Composite slump-loss-resistant polycarboxylic acid water reducing agent and preparation method thereof |
| CN102815882A (en) * | 2012-08-03 | 2012-12-12 | 山西科腾环保科技有限公司 | High-performance water reducer of polycarboxylic acid, and preparation method thereof |
| CN103183793A (en) * | 2013-03-26 | 2013-07-03 | 武汉市联合石油化工有限责任公司 | Synthetic method of polycarboxylic acid type highly slump loss resistant water-reducing agent |
-
2013
- 2013-09-12 CN CN201310416209.1A patent/CN103483504B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1655272A1 (en) * | 2004-11-04 | 2006-05-10 | Mapei S.p.A. | Superplasticizers for extending the workability of mortars |
| CN101735411A (en) * | 2010-01-08 | 2010-06-16 | 北京工业大学 | Method for preparing sustained-release polycarboxylic water reducer |
| CN101913793A (en) * | 2010-08-19 | 2010-12-15 | 上海三瑞高分子材料有限公司 | Polyocarboxylic acid high-performance water reducer |
| CN102515616A (en) * | 2011-11-24 | 2012-06-27 | 上海大学 | Composite slump-loss-resistant polycarboxylic acid water reducing agent and preparation method thereof |
| CN102491678A (en) * | 2011-11-28 | 2012-06-13 | 新疆西建新材料科技有限公司 | Modified polycarboxylic high performance water reducer and its production method and application method |
| CN102815882A (en) * | 2012-08-03 | 2012-12-12 | 山西科腾环保科技有限公司 | High-performance water reducer of polycarboxylic acid, and preparation method thereof |
| CN103183793A (en) * | 2013-03-26 | 2013-07-03 | 武汉市联合石油化工有限责任公司 | Synthetic method of polycarboxylic acid type highly slump loss resistant water-reducing agent |
Non-Patent Citations (1)
| Title |
|---|
| 王明丽等: "聚羧酸系高效减水剂合成工艺研究现状", 《混凝土》, no. 6, 15 June 2007 (2007-06-15), pages 65 - 67 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177558A (en) * | 2014-08-26 | 2014-12-03 | 山东宏艺科技股份有限公司 | polycarboxylate-type water-reducer and preparation method thereof |
| CN105801773A (en) * | 2014-12-29 | 2016-07-27 | 辽宁奥克化学股份有限公司 | Comb-type polymer and its preparation method and use as water reducer |
| CN105801773B (en) * | 2014-12-29 | 2018-07-13 | 辽宁奥克化学股份有限公司 | A kind of comb-shaped polymer, preparation method and the purposes as water-reducing agent |
| CN104710310A (en) * | 2015-01-23 | 2015-06-17 | 四川同舟化工科技有限公司 | O-maleoyl lactate compound, preparation method thereof, and application of compound in synthesis of polycarboxylic superplasticizers |
| CN104692699A (en) * | 2015-02-05 | 2015-06-10 | 石家庄市长安育才建材有限公司 | Early strength type ether polycarboxylate superplasticizer and preparation method thereof |
| CN104692699B (en) * | 2015-02-05 | 2017-03-29 | 石家庄市长安育才建材有限公司 | A kind of early-strength ethers polycarboxylic acid water reducing agent and preparation method thereof |
| US9453097B2 (en) | 2015-02-15 | 2016-09-27 | Beijing University Of Technology | Method for preparation of polycarboxylate superplasticizer by graft copolymerization of fatty acid vinyl ester onto acrylate polymer |
| CN106008849A (en) * | 2016-05-26 | 2016-10-12 | 四川恒泽建材有限公司 | Water reducing agent polymerized from polyethenoxy ethers with different molecular weights and preparation method thereof |
| CN106632881A (en) * | 2016-09-29 | 2017-05-10 | 湖北工业大学 | Low water-reducing and high slump loss resistant type polycarboxylate superplasticizer master batch |
| CN106478891A (en) * | 2016-10-27 | 2017-03-08 | 湖南大学 | A kind of polyurethane-modified high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof |
| CN106478891B (en) * | 2016-10-27 | 2018-11-06 | 湖南大学 | A kind of polyurethane-modified high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof |
| CN108329471A (en) * | 2017-01-19 | 2018-07-27 | 天津大学 | A kind of lithium-sulphur cell positive electrode active material prenol-sulphur copolymer and preparation method |
| CN106893047A (en) * | 2017-02-08 | 2017-06-27 | 山东卓星化工有限公司 | The method that solid polycarboxylic acid water reducing agent is prepared using organic oxidation reduction system |
| CN110003405A (en) * | 2019-04-24 | 2019-07-12 | 四川同舟化工科技有限公司 | Comprehensive high-performance polycarboxylic acids diminishing |
| WO2022194996A1 (en) | 2021-03-17 | 2022-09-22 | Sika Technology Ag | Copolymers useful to retain high slump flow of mineral binder composition, their production and use |
| EP4306495A1 (en) | 2022-07-12 | 2024-01-17 | Sika Technology AG | Copolymers of carboxylates and polyethers comprising polyether side chains of different length, and use thereof in mineral binder compositions |
| WO2024012776A1 (en) | 2022-07-12 | 2024-01-18 | Sika Technology Ag | Copolymers of carboxylates and polyethers comprising polyether side chains of different length, and use thereof in mineral binder compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103483504B (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103483504B (en) | The method of polycarboxylate water-reducer is prepared in the polyether macromonomer combination of two kinds of structures | |
| CN102358768B (en) | Modified ether polycarboxylic acid water reducing agent and preparation method thereof | |
| CN102603996B (en) | Ether type polycarboxylic acid slump retaining agent and preparation method thereof | |
| CN108059697B (en) | Preparation method of polycarboxylate superplasticizer with regular sequence structure | |
| CN103183795B (en) | Low air content polycarboxylic acid water reducer and preparation method thereof | |
| CN104926183A (en) | High-adaptability and high-performance polycarboxylic water-reducing agent and preparation method for same | |
| CN101830663B (en) | Collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN106699988B (en) | A kind of polycarboxylic-acid polymeric superplasticizer and preparation method thereof | |
| CN103613306A (en) | Hyperbranched poly(amine-ester) structure-containing polycarboxylic water reducer and preparation method thereof | |
| CN103992442A (en) | Preparation method and application for amphoteric polycarboxylate water reducer containing anions and cations | |
| CN101817657A (en) | Polycarboxylic acid slump retaining agent | |
| CN105111383A (en) | Process for preparing high-performance polycarboxylic acid type water-reducing agent by combined macromonomers at normal temperature | |
| CN103693881A (en) | Polycarboxylic acid water reducer, application and preparation method of polycarboxylic acid water reducer | |
| CN102503221B (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| CN102408526A (en) | Low-air entraining slow-settling polycarboxylate water reducer and preparation method thereof | |
| CN103554392A (en) | Thickener copolymer as well as preparation method and application thereof | |
| CN103554387A (en) | Thickener copolymer as well as preparation method and application thereof | |
| CN103183797B (en) | A kind of end alkenyl polyether and its preparation method and application | |
| CN102206058B (en) | Ultra-high efficiency polycarboxylate water reducer and preparation method thereof | |
| CN106496442A (en) | A kind of high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof | |
| CN102173641A (en) | Super-efficient carboxylic acid water reducer without thermal energy consumption | |
| CN102516475B (en) | Polycarboxylic concrete water reducer | |
| CN108264615B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN105271905A (en) | Slump retention agent and preparation method thereof | |
| CN104003644B (en) | The production technique of polycarboxylate water-reducer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |