CN107602764B - Hyperbranched copolymer ceramic reinforcing agent and preparation method and application thereof - Google Patents
Hyperbranched copolymer ceramic reinforcing agent and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 62
- 239000012744 reinforcing agent Substances 0.000 title claims abstract description 52
- 229920001577 copolymer Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 14
- -1 acryloxy Chemical group 0.000 claims abstract description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001263 acyl chlorides Chemical group 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- FFPWTXLPZHPZNT-UHFFFAOYSA-N P(=O)(O)(O)O.C(C=C)(=O)OCCCO[Na] Chemical compound P(=O)(O)(O)O.C(C=C)(=O)OCCCO[Na] FFPWTXLPZHPZNT-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- XDFFVDDBWQREAJ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCOC(=O)C=C XDFFVDDBWQREAJ-UHFFFAOYSA-M 0.000 claims description 3
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 3
- QMAXTOJEYXYJSE-UHFFFAOYSA-N P(=O)(O)(O)O.C(C=C)(=O)OCCCCO[Na] Chemical compound P(=O)(O)(O)O.C(C=C)(=O)OCCCCO[Na] QMAXTOJEYXYJSE-UHFFFAOYSA-N 0.000 claims description 2
- FMHDGGKVRGHOLX-UHFFFAOYSA-N P(=O)(O)(O)O.C(C=C)(=O)OCCO[Na] Chemical compound P(=O)(O)(O)O.C(C=C)(=O)OCCO[Na] FMHDGGKVRGHOLX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- XSIQSWHENMREAF-UHFFFAOYSA-N ethylsulfanylmethanedithioic acid Chemical group CCSC(S)=S XSIQSWHENMREAF-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- IXAOZLQUOVRCEO-UHFFFAOYSA-N methylsulfanylmethanedithioic acid Chemical group CSC(S)=S IXAOZLQUOVRCEO-UHFFFAOYSA-N 0.000 claims description 2
- OETRDPZIXKVAQS-UHFFFAOYSA-N propylsulfanylmethanedithioic acid Chemical group CCCSC(S)=S OETRDPZIXKVAQS-UHFFFAOYSA-N 0.000 claims description 2
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 2
- 239000012989 trithiocarbonate Substances 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 abstract 1
- 238000006062 fragmentation reaction Methods 0.000 abstract 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 238000005336 cracking Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- IPQLYEGIWSAJRD-UHFFFAOYSA-N P(=O)(O)(O)O.C(C=C)(=O)OCC[Na] Chemical compound P(=O)(O)(O)O.C(C=C)(=O)OCC[Na] IPQLYEGIWSAJRD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ZHAONEHNCCQNSC-UHFFFAOYSA-M ethyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C(C)=C ZHAONEHNCCQNSC-UHFFFAOYSA-M 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a hyperbranched copolymer ceramic reinforcing agent and a preparation method and application thereof, wherein the hyperbranched copolymer ceramic reinforcing agent is synthesized by adopting an RAFT (reversible addition-fragmentation chain transfer) aqueous solution polymerization method, and is a hyperbranched polymer which takes polyethyleneimine as a center and takes acryloxy alkoxy phosphate monomers and cationic monomer copolymers as arms, the average molecular weight is 10000-50000, and the molecular weight polydispersity is less than 1.25.
Description
Technical Field
The invention relates to a ceramic reinforcing agent, in particular to a hyperbranched copolymer ceramic reinforcing agent and a preparation method and application thereof, belonging to the technical field of ceramic reinforcing agent synthesis.
Background
In the industrial production of ceramics, blanks are a very important link, which directly affects the subsequent processing of the ceramic production (such as blank forming, drying, glazing, printing, firing, etc.). The drying strength of the blank is an important index, and has important influence on the yield and quality of the product. China, as a large country for producing building ceramics, has formed a plurality of larger ceramics, because of the influence of local ceramic blank raw materials and the difference of physical and chemical properties of the ceramic raw materials in different production areas, the use amount of clay raw materials is limited due to the process limitation, the strength of the blank after drying is poor, and the requirement of the production process is difficult to achieve by increasing the forming pressure. Particularly, in recent years, the yield of high-quality plastic clay (such as black mud and white mud in Guangdong province) is less and less, under the condition, a high-performance green body reinforcing agent is produced at the same time, and most ceramic production enterprises nowadays introduce the green body reinforcing agent into a green body as an additive, so that the green body and dry body strength is improved, and the production quality of products is improved.
Chinese patent CN201410834890.6 discloses an acrylamide grafted corn starch ceramic reinforcing agent and a preparation method and application thereof, the invention takes starch as a main synthetic raw material, has wide source and no pollution, and is cleaner and more green compared with other reinforcing agents; overcomes the defects of poor processing performance, difficult dispersion at low temperature, poor permeability, higher price of polyacrylamide, pollution of residual monomers, limitation of use by various conditions and the like of the natural starch; the starch pre-gelatinization operation is simple, the grafting synthesis process is simple, and the industrial production is easy to realize. But because the enhancer of the invention takes corn starch as the main enhancing component, the invention has the defect of large addition amount; meanwhile, the traditional free radical polymerization is adopted during synthesis, so that the reinforcing agent has wide molecular weight distribution and unstable performance.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention provides a hyperbranched copolymer ceramic reinforcing agent.
The invention also aims to provide a preparation method of the hyperbranched copolymer ceramic reinforcing agent.
The invention also aims to provide application of the hyperbranched copolymer ceramic reinforcing agent in ceramic body slurry.
The hyperbranched copolymer ceramic reinforcing agent is a hyperbranched polymer taking polyethyleneimine as a center and taking an acryloxy alkoxy phosphate monomer and a cationic monomer copolymer as arms, has an average molecular weight of 10000-50000, a molecular weight polydispersity coefficient of less than 1.25, and has a structural general formula as follows, wherein m is 2-4, n: 5-10, p is 8-25:
the invention relates to a hyperbranched copolymer ceramic reinforcing agent, and an RAFT preparation method thereof comprises the following steps:
(1) synthesis of hyperbranched RAFT reagent: dissolving 5-8 parts of trithioester containing acyl chloride groups in 25-40 parts of organic solvent, and marking as a solution I; adding 20-30 parts of hyperbranched polyethyleneimine into a reactor, heating to 40-60 ℃ under stirring, then dropwise adding the solution I, continuing to react for 3-6 hours at 40-60 ℃ after 0.5-1 hour of dropwise addition, adding an ammonia water solution for precipitation, washing with an organic solvent, and drying in vacuum to obtain a hyperbranched RAFT reagent;
(2) RAFT polymerisation: adding 20-30 parts of acryloyloxy alkoxy phosphate monomers, 5-10 parts of cationic monomers, 1-5 parts of (1) hyperbranched RAFT reagent, 60-80 parts of water and 0.5-3 parts of reducing agent into a reactor, fully dissolving and uniformly mixing, heating to 45-65 ℃, dropwise adding 6-12 parts of 6-10% initiator aqueous solution, continuously reacting for 2-4 h after 10-30 min dropwise adding, cooling to room temperature, drying, washing, drying and granulating the copolymer ceramic reinforcing agent solution to obtain the hyperbranched copolymer ceramic reinforcing agent.
The trithiocarbonate containing acyl chloride group is at least one of 2- (ethyl trithiocarbonate group) -2-methylpropanoyl chloride, 2- (propyl trithiocarbonate group) -2-methylpropanoyl chloride and 2- (methyl trithiocarbonate group) -2-methylpropanoyl chloride.
The organic solvent is at least one of butanone, cyclohexanone, acetone, butyl acetate and butyl acetate.
The number average molecular weight of the hyperbranched polyethyleneimine is 400-600.
The acryloyloxy alkyl phosphate is at least one of acryloyloxy ethoxy sodium phosphate, acryloyloxy propoxy sodium phosphate and acryloyloxy butoxy sodium phosphate.
The cationic monomer is at least one of acryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium bromide, methacryloyloxyethyl trimethyl ammonium chloride and methacryloyloxyethyl dimethyl ethyl ammonium chloride.
The reducing agent is at least one of ferrous chloride, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium hypophosphite and sodium bisulfite.
The initiator is at least one of hydrogen peroxide, tert-butyl hydroperoxide, 2' -azo (2-methyl propyl amidine) dihydrochloride and ammonium persulfate.
Compared with the prior art, the hyperbranched copolymer ceramic reinforcing agent has the following advantages or beneficial effects: (1) the hyperbranched copolymer ceramic reinforcing agent is prepared by RAFT polymerization for the first time, and the polydispersity index of the copolymer is less than 1.25, so that the reinforcing agent has stable performance; (2) the copolymer ceramic reinforcing agent has a hyperbranched structure, contains phosphate anions with a dispersing effect, and does not produce a thickening effect on a ceramic blank slurry system and influence the normal parameters of the system when added into the ceramic blank slurry system; (3) the hyperbranched copolymer achieves the effect of high-efficiency item increase through the winding, coating and other actions among ceramic blank particles, and macroscopically shows that after the system is dehydrated and cured, the blank strength is increased, and the yield is increased.
Detailed Description
The hyperbranched copolymer ceramic reinforcing agent, the preparation method and the application thereof are further described by combining with the examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
The invention relates to a hyperbranched copolymer ceramic reinforcing agent, and an RAFT preparation method thereof comprises the following steps:
(1) synthesis of hyperbranched RAFT reagent: dissolving 5.6 parts of 2- (methyl trithiocarbonate) -2-methylpropanoyl chloride in 30 parts of acetone to obtain a solution I; and (2) adding 25 parts of hyperbranched polyethyleneimine into a reactor, heating to 40 ℃ under stirring, dropwise adding the solution I, continuing to react for 6 hours at 40 ℃ after 1 hour of dropwise adding, adding an ammonia water solution for precipitation, washing with acetone, and drying in vacuum to obtain the hyperbranched RAFT reagent.
(2) RAFT polymerisation: adding 26 parts of acryloyloxyethyl sodium phosphate, 5 parts of acryloyloxyethyl trimethyl ammonium chloride, 3 parts of hyperbranched RAFT reagent in the step (1), 80 parts of water, 0.5 part of sodium hypophosphite and 0.5 part of sodium formaldehyde sulfoxylate into a reactor, fully dissolving, uniformly mixing, heating to 55 ℃, dropwise adding 10 parts of 7.5% hydrogen peroxide solution, continuously reacting for 3 hours after 10min dropwise adding, cooling to room temperature, drying, washing, drying and granulating the copolymer ceramic reinforcing agent solution to obtain the hyperbranched copolymer ceramic reinforcing agent.
And (3) performance testing: the enhancement effect of the product is determined according to the practical production method of the sanitary ceramics: uniformly stirring standard slurry of a certain ceramic company in Shandong area, measuring 500ml of slurry by using a measuring cup of 1000ml, adding 0.16g of hyperbranched copolymer ceramic reinforcing agent in the embodiment, stirring for five minutes by using a high-speed stirrer, injecting into a standard inner triangle (side length is 30mm) mould, starting to time by using a stopwatch, uncovering the mould after thirty minutes, wherein the operation temperature is room temperature, the initial cracking time is 24min41s, the final cracking time is 64min14s, and the final cracking length is 14.5 mm; under the same conditions, the slurry without the reinforcing agent is added, the initial crack time is 2min09s, the final crack time is 4min14s, and the final crack length is 25 mm.
Example 2
The invention relates to a hyperbranched copolymer ceramic reinforcing agent, and an RAFT preparation method thereof comprises the following steps:
(1) synthesis of hyperbranched RAFT reagent: dissolving 6.2 parts of 2- (propyltrithiocarbonate) -2-methylpropanoyl chloride in 25 parts of butanone to obtain a solution I; and (2) adding 14 parts of hyperbranched polyethyleneimine into a reactor, heating to 55 ℃ under stirring, dropwise adding the solution I, continuously reacting for 5 hours at 55 ℃ after 0.5 hour of dropwise adding is finished, adding an ammonia water solution for precipitation, washing with butanone, and drying in vacuum to obtain the hyperbranched RAFT reagent.
(2) RAFT polymerisation: adding 24 parts of acryloyloxy propoxy sodium phosphate, 5.3 parts of acryloyloxyethyl trimethyl ammonium bromide, 2 parts of hyperbranched RAFT reagent in the step (1), 65 parts of water and 1.5 parts of sodium bisulfite into a reactor, fully dissolving, uniformly mixing, heating to 65 ℃, dropwise adding 9 parts of 6% ammonium persulfate solution, continuing to react for 2-4 hours after 15min of dropwise addition, cooling to room temperature, drying, washing, drying again and granulating the copolymer ceramic reinforcing agent solution to obtain the hyperbranched copolymer ceramic reinforcing agent.
And (3) performance testing: the enhancement effect of the product is determined according to the practical production method of the sanitary ceramics: uniformly stirring standard slurry of a certain ceramic company in Shandong area, measuring 500ml of slurry by using a measuring cup of 1000ml, adding 0.16g of hyperbranched copolymer ceramic reinforcing agent in the embodiment, stirring for five minutes by using a high-speed stirrer, injecting into a standard inner triangle (side length is 30mm) mould, starting to time by using a stopwatch, uncovering the mould after thirty minutes, wherein the operation temperature is room temperature, the initial cracking time is 29min50s, the final cracking time is 70min11s, and the final cracking length is 14 mm; under the same conditions, the slurry without the reinforcing agent is added, the initial crack time is 2min09s, the final crack time is 4min14s, and the final crack length is 25 mm.
Example 3
The invention relates to a hyperbranched copolymer ceramic reinforcing agent, and an RAFT preparation method thereof comprises the following steps:
(1) synthesis of hyperbranched RAFT reagent: dissolving 7 parts of 2- (propyltrithiocarbonate) -2-methylpropanoyl chloride in 37 parts of butyl acetate, and marking as a solution I; and (2) adding 22 parts of hyperbranched polyethyleneimine into a reactor, heating to 60 ℃ under stirring, dropwise adding the solution I, continuing to react for 4.5 hours at 60 ℃ after 1 hour of dropwise adding, adding an ammonia water solution for precipitation, washing with butyl acetate, and drying in vacuum to obtain the hyperbranched RAFT reagent.
(2) RAFT polymerisation: adding 28 parts of sodium methacryloxybutoxy phosphate, 8 parts of methacryloxyethyl trimethyl ammonium chloride, 4 parts of the hyperbranched RAFT reagent in the step (1), 80 parts of water and 1.3 parts of ferrous sulfate into a reactor, fully dissolving, uniformly mixing, heating to 50 ℃, dropwise adding 11 parts of 9% hydrogen peroxide solution, continuing to react for 3.5 hours after 30min is completed, cooling to room temperature, drying, washing, drying again and granulating the copolymer ceramic reinforcing agent solution to obtain the hyperbranched copolymer ceramic reinforcing agent.
And (3) performance testing: the enhancement effect of the product is determined according to the practical production method of the sanitary ceramics: uniformly stirring standard slurry of a certain ceramic company in Shandong area, measuring 500ml of slurry by using a measuring cup of 1000ml, adding 0.16g of hyperbranched copolymer ceramic reinforcing agent in the embodiment, stirring for five minutes by using a high-speed stirrer, injecting into a standard inner triangle (side length is 30mm) mould, starting to time by using a stopwatch, uncovering the mould after thirty minutes, wherein the operation temperature is room temperature, the initial cracking time is 27min42s, the final cracking time is 65min26s, and the final cracking length is 16 mm; under the same conditions, no reinforcing agent slurry is added, the initial crack time is 2min9s, the final crack time is 4min14s, and the final crack length is 25 mm.
Claims (8)
1. The hyperbranched copolymer ceramic reinforcing agent is characterized in that the hyperbranched copolymer ceramic reinforcing agent is a hyperbranched polymer which takes polyethyleneimine as a center and takes acryloxy alkoxy phosphate monomers and cationic monomer copolymers as arms, has an average molecular weight of 10000-50000 and a molecular weight polydispersity index of less than 1.25, and has the following structural general formula, wherein m is 2-4, n: 5-10, p is 8-25:
2. a method for preparing the hyperbranched copolymer ceramic reinforcing agent as defined in claim 1, comprising the steps of:
(1) synthesis of hyperbranched RAFT reagent: dissolving 5-8 parts of trithioester containing acyl chloride group in 25-40 parts of organic solvent, and marking as solution
(ii) a Adding 20-30 parts of hyperbranched polyethyleneimine into a reactor, heating to 40-60 ℃ while stirring, and then dropwise adding the solution
After 0.5-1 h of dropwise addition, continuously reacting for 3-6 h at 40-60 ℃, adding an ammonia water solution for precipitation, washing with an organic solvent, and drying in vacuum to obtain a hyperbranched RAFT reagent;
(2) RAFT polymerisation: adding 20-30 parts of acryloyloxy alkoxy phosphate monomers, 5-10 parts of cationic monomers, 1-5 parts of (1) hyperbranched RAFT reagent, 60-80 parts of water and 0.5-3 parts of reducing agent into a reactor, fully dissolving, uniformly mixing, heating to 45-65 ℃, dropwise adding 6-12 parts of 6-10% initiator aqueous solution, continuing to react for 2-4 h after 10-30 min is finished, cooling to room temperature, drying, washing, drying and granulating the copolymer ceramic reinforcing agent solution to obtain the hyperbranched copolymer ceramic reinforcing agent;
the acryloxy alkyl phosphate monomer is at least one of acryloxy ethoxy sodium phosphate, acryloxy propoxy sodium phosphate and acryloxy butoxy sodium phosphate;
the cationic monomer is at least one of acryloyloxyethyl trimethyl ammonium chloride and acryloyloxyethyl trimethyl ammonium bromide.
3. The method for preparing a hyperbranched copolymer ceramic reinforcing agent as claimed in claim 2, wherein: the trithiocarbonate containing acyl chloride group is at least one of 2- (ethyl trithiocarbonate group) -2-methylpropanoyl chloride, 2- (propyl trithiocarbonate group) -2-methylpropanoyl chloride and 2- (methyl trithiocarbonate group) -2-methylpropanoyl chloride.
4. The method for preparing a hyperbranched copolymer ceramic reinforcing agent as claimed in claim 2, wherein: the organic solvent is at least one of butanone, cyclohexanone, acetone and butyl acetate.
5. The method for preparing a hyperbranched copolymer ceramic reinforcing agent as claimed in claim 2, wherein: the number average molecular weight of the hyperbranched polyethyleneimine is 400-600.
6. The method for preparing a hyperbranched copolymer ceramic reinforcing agent as claimed in claim 2, wherein: the reducing agent is at least one of ferrous chloride, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium hypophosphite and sodium bisulfite.
7. The method for preparing a hyperbranched copolymer ceramic reinforcing agent as claimed in claim 2, wherein: the initiator is at least one of hydrogen peroxide, tert-butyl hydroperoxide, 2' -azo (2-methyl propyl amidine) dihydrochloride and ammonium persulfate.
8. Use of a hyperbranched copolymer ceramic reinforcing agent as defined in claim 1 or a hyperbranched copolymer ceramic reinforcing agent prepared by the preparation method as defined in claim 2, wherein: the hyperbranched copolymer ceramic reinforcing agent is applied to ceramic body slurry.
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| CN101514107B (en) * | 2009-03-13 | 2013-01-02 | 中国科学院上海硅酸盐研究所 | Mixed initiating system for increasing the stability of gelatin casting molding ceramic slurry and use method thereof |
| CN105439299B (en) * | 2015-11-10 | 2018-04-24 | 西安建筑科技大学 | A kind of preparation method and application of hyperbranched polyethyleneimine copolymer water treatment agent |
| CN106432599A (en) * | 2016-09-29 | 2017-02-22 | 陕西科技大学 | Hyperbranched polyacrylamide and preparation method thereof |
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2017
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Denomination of invention: A hyperbranched copolymer ceramic reinforcing agent and its preparation method and application Effective date of registration: 20231212 Granted publication date: 20200214 Pledgee: China Postal Savings Bank Limited by Share Ltd. Chaozhou branch Pledgor: Guangdong Zhijie Sanitary Ware Co.,Ltd. Registration number: Y2023980070884 |