CN116675863A - Corrosion-resistant high-strength silane modified polyester resin and processing technology thereof - Google Patents
Corrosion-resistant high-strength silane modified polyester resin and processing technology thereof Download PDFInfo
- Publication number
- CN116675863A CN116675863A CN202310802354.7A CN202310802354A CN116675863A CN 116675863 A CN116675863 A CN 116675863A CN 202310802354 A CN202310802354 A CN 202310802354A CN 116675863 A CN116675863 A CN 116675863A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- parts
- heating
- resin
- modified polyester
- 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
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 88
- 239000004645 polyester resin Substances 0.000 title claims abstract description 88
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 39
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 238000005516 engineering process Methods 0.000 title abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 claims abstract description 39
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010936 titanium Substances 0.000 claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 claims abstract description 21
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 78
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 22
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 21
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 20
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000005639 Lauric acid Substances 0.000 claims description 11
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- FJWRGPWPIXAPBJ-UHFFFAOYSA-N diethyl(dimethyl)silane Chemical compound CC[Si](C)(C)CC FJWRGPWPIXAPBJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000006011 modification reaction Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- -1 alkoxy silane Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to corrosion-resistant high-strength silane modified polyester resin and a processing technology thereof. The invention utilizes titanium-containing organic silicon resin to modify unsaturated vinyl ester polyester resin under the action of catalyst to obtain the modified polyester resin with corrosion resistance, high Tg value and high strength. Wherein the titanium-containing organic silicon resin is synthesized by dimethyl diethyl silane and mono-phenyl triethoxy silane and butyl titanate. Vinyl polyester resin is synthesized by epoxy resin and acrylic acid. The catalyst adopts tributyltin trilaurate, and has better promotion effect on modification reaction. Meanwhile, benzene rings containing amino groups are grafted into the vinyl polyester resin, so that the synthetic polyester resin has higher heat resistance and better adhesive force.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to corrosion-resistant high-strength silane modified polyester resin and a processing technology thereof.
Background
Corrosion is a subject of absolute environmental protection, and therefore, corrosion protection is particularly important in the present day where resource conservation is increasingly emphasized and rational utilization of resources is advocated.
Equipment and material corrosion occurs in a variety of situations, and in order to protect such equipment from corrosion, it is now common practice to coat some of the material surfaces with a coating to reduce the rate at which the material is corroded. Silicone resins themselves have good properties such as heat resistance, weather resistance, etc., but the problems of poor adhesion, difficulty in curing, etc. are not negligible. Therefore, the invention firstly grafts the polyester resin, so that the adhesive force of the polyester resin is enhanced, the heat resistance is improved, and the curing performance is also improved. Adding titanium-containing organosilicon for modification, so that the resin has better corrosion resistance.
Disclosure of Invention
The invention aims to provide a corrosion-resistant high-strength silane modified polyester resin and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the corrosion-resistant high-strength silane modified polyester resin is prepared from 50-70 parts of unsaturated vinyl ester polyester resin, 20-50 parts of titanium-containing organic silicon resin and 2.5-3.5 parts of tributyltin trilaurate.
Further, the unsaturated vinyl ester polyester resin production comprises the following steps:
s1, adding p-aminophenol into epoxy resin, heating to 90-110 ℃, dropwise adding sodium hydroxide solution, keeping the temperature for 1-4 hours after dropwise adding, washing with deionized water, adding epichlorohydrin, heating to 45-55 ℃, adding benzyl triethyl ammonium chloride, heating to 80-100 ℃, reacting for 4-8 hours, dropwise adding sodium hydroxide aqueous solution, continuing reacting for 3-8 hours, finishing the reaction, purifying and washing to obtain amino epoxy resin;
s2, heating the obtained amino epoxy resin to 60-100 ℃, mixing N-N dimethylbenzylamine, hydroquinone and acrylic acid, then dripping the mixture into the amino epoxy resin for 20-50min, heating to 90-120 ℃ for continuous reaction, detecting an acid value at regular time, and stopping until the acid value is 3-7 mg KOH/g, thus obtaining the unsaturated vinyl ester polyester resin.
Further, in S1, according to parts by weight, 18-20 parts of epoxy resin, 10-20 parts of p-aminophenol, 60-80 parts of epichlorohydrin and 1-2 parts of benzyl triethyl ammonium chloride.
Further, in S2, 18 to 20 parts of amino epoxy resin, 0.5 to 2 parts of N-N dimethylbenzylamine, 0.1 to 0.2 part of hydroquinone and 60 to 80 parts of acrylic acid are calculated according to parts by weight.
Further, the preparation of the titanium-containing organic resin comprises the following steps:
adding butyl titanate into dimethylbenzene to prepare a solution, mixing dimethyl diethoxy silane, mono-phenyl triethoxy silane, hydrochloric acid and absolute ethyl alcohol, heating to 50-70 ℃, dropwise adding deionized water, hydrolyzing, preserving heat for 1-4 h, adding the prepared butyl titanate dimethylbenzene solution, dropwise adding deionized water, preserving heat for 1-4 h, performing rotary evaporation, removing ethanol and dimethylbenzene, heating to 100-140 ℃, and preserving heat for 0.5-3 h.
Further, according to the weight portions, 8 to 15 portions of dimethyl diethoxy silane, 25 to 35 portions of mono phenyl triethoxy silane, 0.1 to 1g of hydrochloric acid and 15 to 25g of butyl titanate.
Further, the preparation method of the tributyltin trilaurate comprises the following steps: firstly drying monobutyl tin oxide, heating lauric acid to 70-100 ℃, adding the dried monobutyl tin oxide to react for 2-5 h at 60-90 ℃, heating to 80-100 ℃, and preserving heat for 2-5 h to obtain the tributyltin trilaurate.
Further, 50-70 parts of lauric acid and 8-18 parts of monobutyl tin oxide.
The steps of the silane modified polyester resin are as follows:
mixing unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 160-200 ℃, preserving heat for 1-2h, slowly heating to 160-200 ℃, preserving heat for 2-4h, stirring for 10-40 min under vacuum condition, cooling and discharging to obtain the silane modified polyester resin.
Compared with the prior art, the invention has the following beneficial effects:
1. in the invention, amino and benzene rings are introduced into the main chain when the saturated vinyl ester polyester resin is synthesized. The introduction of anilino groups is easier to generate polycondensation reaction and crosslinking, and can improve the heat resistance, mechanical property and chemical resistance of the whole epoxy resin. Meanwhile, vinyl ester polyester resin is synthesized by taking vinyl acid as a substrate, so that the epoxy resin is easier to cure, and the epoxy resin can be cured by photo-curing or thermal curing.
2. In the synthetic process of the organic silicon resin, alkoxy silane is adopted for hydrolytic polycondensation, alkoxy is reserved in the main chain and is blocked by ethoxy, no harmful substances are generated in the hydrolysis process, and the organic silicon resin is environment-friendly. Meanwhile, the synthesis route is simple and easy to operate.
3. In the process of copolymerization modification, the ethoxy in the organic silicon resin disappears, and the titanium-containing organic silicon resin is successfully connected to the unsaturated polyester resin, so that the compatibility of the organic silicon resin and the unsaturated polyester resin is improved. The modified polyester resin has good heat resistance and corrosion resistance.
Detailed Description
The epoxy resin used in the invention is epoxy resin E-51, the model is CYD-128, and the epoxy resin is purchased from Yueyang Baling petrochemical industry; dimethyldiethoxysilane is available from Beijing Da Tian Fengta chemical technology Co., ltd; mono-phenyl triethoxysilane is available from Beijing da Tian Fengta chemical technology Co., ltd; butyl titanate was purchased from the metallocene chemical reagent plant in the Tianjin city; monobutyl tin oxide is purchased from Annaiji chemistry; lauric acid was purchased from carbofuran technologies.
Example 1.
The corrosion-resistant high-strength silane modified polyester resin is prepared from 55 parts of unsaturated vinyl ester polyester resin, 25 parts of titanium-containing organic silicon resin and 2.5 parts of catalyst.
The preparation method of the unsaturated vinyl ester polyester resin comprises the following steps:
s1, adding 11g of p-aminophenol into 18.9g of epoxy resin, heating to 105 ℃, dropwise adding 20% sodium hydroxide solution, preserving heat for 2 hours after dropwise adding, washing with deionized water, adding 66g of epichlorohydrin, heating to 50 ℃, adding 1.1g of benzyl triethyl ammonium chloride, heating to 90 ℃, reacting for 6 hours, dropwise adding 18g of 40% sodium hydroxide solution, continuing to react for 4.5 hours, finishing the reaction, purifying and washing, and obtaining the amino epoxy resin.
S2, heating 20g of the amino epoxy resin obtained in the S1 to 80 ℃, and dropwise adding a mixed solution of 1.1g of N-N dimethylbenzylamine, 0.13g of hydroquinone and 74g of acrylic acid within 0.5 h. And (3) heating to 110 ℃ to continue the reaction, then titrating the acid value of the reaction system every 0.5h, and stopping the reaction when the acid value is 5mgKOH/g to obtain the unsaturated vinyl ester polyester resin.
The preparation method of the titanium-containing organic resin comprises the following steps:
11.2g of dimethyldiethoxysilane, 28g of monophenyl triethoxysilane, 0.6g of hydrochloric acid and 30g of absolute ethyl alcohol are mixed, the temperature is raised to 65 ℃, 7g of deionized water is added dropwise, and the temperature is kept for 2 hours. 19g of butyl titanate is added into dimethylbenzene to prepare dimethylbenzene solution, 3g of deionized water is added dropwise, the temperature is kept for 2 hours, the vacuum rotary evaporation is carried out at 50 ℃, ethanol and dimethylbenzene are removed, the temperature is heated to 120 ℃, and the temperature is kept for 1 hour, so that the titanium-containing organic resin is obtained.
The preparation method of the catalyst comprises the following steps:
and (3) drying the monobutyl tin oxide at 110 ℃ for 1h, heating 60.4g of lauric acid to 80 ℃, adding 9.6g of monobutyl tin oxide to react for 3.5h at 85 ℃, heating to 95 ℃, and preserving heat for 4h to obtain the tributyltin trilaurate catalyst.
The step of silane modifying the polyester resin comprises:
adding unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 170 ℃, preserving heat for 1h, slowly heating to 180 ℃, and preserving heat for 3h; stirring for 20min under vacuum condition, cooling and discharging to obtain the silane modified polyester resin.
Example 2.
The corrosion-resistant high-strength silane modified polyester resin is prepared from 55 parts of unsaturated vinyl ester polyester resin, 25 parts of titanium-containing organic silicon resin and 2.5 parts of catalyst.
The unsaturated vinyl ester polyester resin preparation comprises the following steps:
s1, adding 11g of p-aminophenol into 18.9g of epoxy resin, heating to 90 ℃, dropwise adding 20% sodium hydroxide solution, preserving heat for 2 hours after dropwise adding, washing with deionized water, adding 66g of epichlorohydrin, heating to 45 ℃, adding 1.1g of benzyl triethyl ammonium chloride, heating to 80 ℃, reacting for 5 hours, dropwise adding 18g of 40% sodium hydroxide solution, continuing reacting for 3.5 hours, finishing the reaction, purifying and washing, and obtaining the amino epoxy resin.
S2, heating 20g of the amino epoxy resin obtained in the S1 to 70 ℃, and dropwise adding a mixed solution of 1.1-g N-N dimethylbenzylamine, 0.13g of hydroquinone and 74g of acrylic acid for 20 min. The reaction was continued by heating to 90℃and then the acid value was measured every 0.5 hour, and the reaction was stopped when the acid value was 5mg KOH/g, to obtain an unsaturated vinyl ester polyester resin.
The preparation of the titanium-containing organic resin comprises the following steps:
11.2g of dimethyldiethoxysilane, 28g of monophenyl triethoxysilane, 0.6g of hydrochloric acid and 30g of absolute ethyl alcohol are mixed, the temperature is raised to 50 ℃, 7g of deionized water is added dropwise, and the temperature is kept for 2 hours. 19g of butyl titanate is added into dimethylbenzene to prepare dimethylbenzene solution, 3g of deionized water is added dropwise, the temperature is kept for 1h, the vacuum rotary evaporation is carried out at 50 ℃, ethanol and dimethylbenzene are removed, the temperature is heated to 100 ℃, and the temperature is kept for 1h, so that the titanium-containing organic resin is obtained.
The preparation method of the catalyst comprises the following steps:
and (3) drying the monobutyl tin oxide at 110 ℃ for 1h, heating 60.4g of lauric acid to 70 ℃, adding 9.6g of monobutyl tin oxide to react for 3.5h at 70 ℃, heating to 95 ℃, and preserving heat for 4h to obtain the tributyltin trilaurate catalyst.
The step of silane modified polyester resin:
adding unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 160 ℃, preserving heat for 1.5h, slowly heating to 170 ℃ and preserving heat for 2h; stirring for 20min under vacuum condition, cooling and discharging to obtain the silane modified polyester resin.
Example 3.
The corrosion-resistant high-strength silane modified polyester resin is prepared from 55 parts of unsaturated vinyl ester polyester resin, 25 parts of titanium-containing organic silicon resin and 2.5 parts of catalyst.
The preparation method of the unsaturated vinyl ester polyester resin comprises the following steps:
s1, adding 11g of p-aminophenol into 18.9g of epoxy resin, heating to 95 ℃, dropwise adding 20% sodium hydroxide solution, preserving heat for 4 hours after dropwise adding, washing with deionized water, adding 66g of epichlorohydrin, heating to 45 ℃, adding 1.1g of benzyl triethyl ammonium chloride, heating to 85 ℃, reacting for 8 hours, dropwise adding 18g of 40% sodium hydroxide aqueous solution, continuing to react for 5 hours, finishing the reaction, purifying and washing, and obtaining the amino epoxy resin.
S2, heating 20g of the amino epoxy resin obtained in the step S1 to 60 ℃, and dropwise adding a mixed solution of 1.1-g N-N dimethylbenzylamine, 0.13g of hydroquinone and 74g of acrylic acid within 0.5 h. And heating to 95 ℃ to continue the reaction, then titrating the acid value of the reaction system every 0.5h, and stopping the reaction when the acid value is 5mg KOH/g to obtain the unsaturated vinyl ester polyester resin.
The preparation method of the titanium-containing organic resin comprises the following steps:
11.2g of dimethyldiethoxysilane, 28g of monophenyl triethoxysilane, 0.6g of hydrochloric acid and 30g of absolute ethyl alcohol are mixed, the temperature is raised to 50 ℃, 7g of deionized water is added dropwise, and the temperature is kept for 2 hours. 19g of butyl titanate is added into dimethylbenzene to prepare dimethylbenzene solution, 3g of deionized water is added dropwise, the temperature is kept for 3 hours, vacuum rotary evaporation is carried out at 50 ℃, ethanol and dimethylbenzene are removed, the temperature is heated to 140 ℃, and the temperature is kept for 0.5 hour, so that the titanium-containing organic resin is obtained.
The preparation method of the catalyst comprises the following steps:
and (3) drying the monobutyl tin oxide at 100 ℃ for 1h, heating 60.4g of lauric acid to 85 ℃, adding 9.6g of monobutyl tin oxide to react for 3.5h at 85 ℃, heating to 100 ℃, and preserving heat for 5h to obtain the tributyltin trilaurate catalyst.
The step of silane modifying the polyester resin comprises:
adding unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 170 ℃, preserving heat for 1.5h, slowly heating to 180 ℃, and preserving heat for 2.5h; stirring for 20min under vacuum condition, cooling and discharging to obtain the silane modified polyester resin.
Example 4.
The corrosion-resistant high-strength silane modified polyester resin is prepared from 55 parts of unsaturated vinyl ester polyester resin, 25 parts of titanium-containing organic silicon resin and 2.5 parts of catalyst.
The unsaturated vinyl ester polyester resin preparation comprises the following steps:
s1, adding 11g of p-aminophenol into 18.9g of epoxy resin, heating to 100 ℃, dropwise adding 20% sodium hydroxide solution, preserving heat for 2 hours after dropwise adding, washing with deionized water, adding 66g of epichlorohydrin, heating to 48 ℃, adding 1.1g of benzyl triethyl ammonium chloride, heating to 98 ℃, reacting for 6 hours, dropwise adding 18g of 40% sodium hydroxide solution, continuing reacting for 7 hours, finishing the reaction, purifying and washing to obtain the amino epoxy resin.
S2, heating 20g of the amino epoxy resin obtained in the step S1 to 90 ℃, and dropwise adding a mixed solution of 1.1-g N-N dimethylbenzylamine, 0.13g of hydroquinone and 74g of acrylic acid for 50 min. And heating to 120 ℃ to continue the reaction, then titrating the acid value of the reaction system every 0.5h, and stopping the reaction when the acid value is 5mg KOH/g to obtain the unsaturated vinyl ester polyester resin.
The preparation of the titanium-containing organic resin comprises the following steps:
11.2g of dimethyldiethoxysilane, 28g of monophenyl triethoxysilane, 0.6g of hydrochloric acid and 30g of absolute ethyl alcohol are mixed, the temperature is raised to 68 ℃, 7g of deionized water is added dropwise, and the temperature is kept for 2 hours. Adding 19g of butyl titanate into dimethylbenzene to prepare a dimethylbenzene solution, dropwise adding 3g of deionized water, preserving heat for 4 hours, performing vacuum rotary evaporation at 50 ℃, removing ethanol and dimethylbenzene, heating to 110 ℃, and preserving heat for 3 hours to obtain the titanium-containing organic resin.
The preparation method of the catalyst comprises the following steps:
and (3) drying the monobutyl tin oxide at 110 ℃ for 1h, heating 60.4g of lauric acid to 80 ℃, adding 9.6g of monobutyl tin oxide to react for 3.5h at 85 ℃, heating to 95 ℃, and preserving heat for 4h to obtain the tributyltin trilaurate catalyst.
The step of silane modifying the polyester resin comprises:
adding unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 170 ℃, preserving heat for 1-2h, slowly heating to 180 ℃, and preserving heat for 2-4h; reacting for 1-2h in a vacuum environment, removing small molecules, stirring for 20min in the vacuum environment, cooling and discharging to obtain the silane modified polyester resin.
Example 5.
The corrosion-resistant high-strength silane modified polyester resin is prepared from 55 parts of unsaturated vinyl ester polyester resin, 25 parts of titanium-containing organic silicon resin and 2.5 parts of catalyst.
The unsaturated vinyl ester polyester resin preparation comprises the following steps:
s1, adding 11g of p-aminophenol into 18.9g of epoxy resin, heating to 100 ℃, dropwise adding 20% sodium hydroxide solution, preserving heat for 2 hours after dropwise adding, washing with deionized water, adding 66g of epichlorohydrin, heating to 55 ℃, adding 1.1g of benzyl triethyl ammonium chloride, heating to 80 ℃, reacting for 6 hours, dropwise adding 18g of 40% sodium hydroxide solution, continuing reacting for 8 hours, finishing the reaction, purifying and washing to obtain the amino epoxy resin.
S2, heating 20g of the amino epoxy resin obtained in the step S1 to 60 ℃, and dropwise adding a mixed solution of 1.1-g N-N dimethylbenzylamine, 0.13g of hydroquinone and 74g of acrylic acid for 20 min. And (3) heating to 110 ℃ to continue the reaction, then titrating the acid value of the reaction system every 0.5h, and stopping the reaction when the acid value is 5mg KOH/g to obtain the unsaturated vinyl ester polyester resin.
The preparation of the titanium-containing organic resin comprises the following steps:
11.2g of dimethyldiethoxysilane, 28g of monophenyl triethoxysilane, 0.6g of hydrochloric acid and 30g of absolute ethyl alcohol are mixed, the temperature is raised to 70 ℃, 7g of deionized water is added dropwise, and the temperature is kept for 3 hours. 19g of butyl titanate is added into dimethylbenzene to prepare dimethylbenzene solution, 3g of deionized water is added dropwise, the temperature is kept for 2 hours, the vacuum rotary evaporation is carried out at 50 ℃, ethanol and dimethylbenzene are removed, the temperature is heated to 120 ℃, and the temperature is kept for 3 hours, so that the titanium-containing organic resin is obtained.
The preparation method of the catalyst comprises the following steps:
and (3) drying the monobutyl tin oxide at 110 ℃ for 1h, heating 60.4g of lauric acid to 75 ℃, adding 9.6g of monobutyl tin oxide to react at 90 ℃ for 5h, heating to 100 ℃, and preserving heat for 2h to obtain the tributyltin trilaurate catalyst.
The step of silane modifying the polyester resin comprises:
adding unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 170 ℃, preserving heat for 2 hours, slowly heating to 180 ℃, preserving heat for 3 hours, stirring for 20 minutes under vacuum condition, cooling and discharging to obtain silane modified polyester resin.
Comparative example 1.
In contrast to example 1, no anilino groups were introduced into the epoxy resin.
The corrosion-resistant high-strength silane modified polyester resin is prepared from 55 parts of unsaturated vinyl ester polyester resin, 25 parts of titanium-containing organic silicon resin and 2.5 parts of catalyst.
The unsaturated vinyl ester polyester resin preparation comprises the following steps:
20g of epoxy resin is heated to 80 ℃, 1.1g of N-N dimethylbenzylamine, 0.13g of hydroquinone and 74g of acrylic acid mixed solution are added dropwise, and the dropwise addition is completed within 0.5 h. And (3) heating to 110 ℃ to continue the reaction, then titrating the acid value of the reaction system every 0.5h, and stopping the reaction when the acid value is 5mg KOH/g to obtain the unsaturated vinyl ester polyester resin.
The preparation of the titanium-containing organic resin comprises the following steps:
11.2g of dimethyldiethoxysilane, 28g of monophenyl triethoxysilane, 0.6g of hydrochloric acid and 30g of absolute ethyl alcohol are mixed, the temperature is raised to 65 ℃, 7g of deionized water is added dropwise, and the temperature is kept for 2 hours. 19g of butyl titanate is added into dimethylbenzene to prepare dimethylbenzene solution, 3g of deionized water is added dropwise, the temperature is kept for 2 hours, the vacuum rotary evaporation is carried out at 50 ℃, ethanol and dimethylbenzene are removed, the temperature is heated to 120 ℃, and the temperature is kept for 1 hour, so that the titanium-containing organic resin is obtained.
The preparation method of the catalyst comprises the following steps:
and (3) drying the monobutyl tin oxide at 110 ℃ for 1h, heating 60.4g of lauric acid to 80 ℃, adding 9.6g of monobutyl tin oxide to react for 3.5h at 85 ℃, heating to 95 ℃, and preserving heat for 4h to obtain the tributyltin trilaurate catalyst.
The step of silane modifying the polyester resin comprises:
adding unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 170 ℃, preserving heat for 1-2h, slowly heating to 180 ℃, and preserving heat for 2-4h; reacting for 1-2h in a vacuum environment, removing small molecules, stirring for 20min in the vacuum environment, cooling and discharging to obtain the silane modified polyester resin.
Comparative example 2.
In contrast to example 1, the polyester resin was not modified.
The corrosion-resistant high-strength silane modified polyester resin is prepared from 55 parts of unsaturated vinyl ester polyester resin, 25 parts of titanium-containing organic silicon resin and 2.5 parts of catalyst.
The unsaturated vinyl ester polyester resin preparation comprises the following steps:
s1, adding 11g of p-aminophenol into 18.9g of epoxy resin, heating to 105 ℃, dropwise adding 20% sodium hydroxide solution, preserving heat for 2 hours after dropwise adding, washing with deionized water, adding 66g of epichlorohydrin, heating to 50 ℃, adding 1.1g of benzyl triethyl ammonium chloride, heating to 90 ℃, reacting for 6 hours, dropwise adding 18g of 40% sodium hydroxide solution, continuing reacting for 3-8 hours, finishing the reaction, purifying and washing to obtain the amino epoxy resin.
S2, heating 20g of the amino epoxy resin obtained in the step S1 to 80 ℃, and dropwise adding a mixed solution of 1.1-g N-N dimethylbenzylamine, 0.13g of hydroquinone and 74g of acrylic acid within 0.5 h. And (3) heating to 110 ℃ to continue the reaction, then titrating the acid value of the reaction system every 0.5h, and stopping the reaction when the acid value is 5mg KOH/g to obtain the unsaturated vinyl ester polyester resin.
Detection test:
polishing the tinplate with sand paper, cleaning with ethanol, and air drying for use. The polyester resins prepared in comparative examples 1 to 2 were coated on the surface of the treated iron sheet to a thickness of 5. Mu.m, and cured at 180℃for 10 minutes.
1. The adhesion of the coating film was measured according to GB/T1720-79 (89).
2. Acid and alkali resistance is detected according to GB/T9274 standard. A 20% sulfuric acid solution and a 20% potassium hydroxide solution were prepared, and poured into two containers, respectively, two thirds of the iron pieces covered with the polyester resin were immersed in the solutions, and the time for which the iron pieces were corroded was observed.
3. Corrosion resistance was tested according to GB/T1771-1991. The test conditions were: the room temperature is 33-37 ℃ and the horizontal plane is 80cm 2 The sedimentation rate is 1-2 mL/h, the concentration of the sodium chloride solution is 50g/L, and the pH value is 6.5-7.2. An iron piece covered with a polyester resin was hung therein, and the time for which the iron piece was corroded was observed.
4. The hardness of the coating film was measured according to GB/T6739-1996 standard.
| Adhesive force strength grade | Acid resistance | Alkali resistance | Neutral salt fog resistance | Hardness grade of application | |
| Example 1 | 1 | 30d | 11d | 25d | 6H |
| Example 2 | 1 | 30d | 12d | 26d | 6H |
| Example 3 | 1 | 30d | 11d | 25d | 6H |
| Example 4 | 1 | 30d | 11d | 24d | 6H |
| Example 5 | 1 | 30d | 11d | 25d | 6H |
| Comparative example 1 | 4 | 28d | 10d | 20d | 5H |
| Comparative example 2 | 3 | 11d | 6d | 9d | 3H |
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A corrosion-resistant high-strength silane modified polyester resin is characterized in that: the silane modified polyester resin is prepared from 50-70 parts of unsaturated vinyl ester polyester resin, 20-50 parts of titanium-containing organic silicon resin and 2.5-3.5 parts of tributyltin trilaurate.
2. The corrosion resistant, high strength silane modified polyester resin of claim 1, wherein: the unsaturated vinyl ester polyester resin preparation comprises the following steps:
s1, adding p-aminophenol into epoxy resin, heating to 90-110 ℃, dropwise adding sodium hydroxide solution, keeping the temperature for 1-4 hours after dropwise adding, washing with deionized water, adding epichlorohydrin, heating to 45-55 ℃, adding benzyl triethyl ammonium chloride, heating to 80-100 ℃, reacting for 4-8 hours, dropwise adding sodium hydroxide aqueous solution, continuing reacting for 3-8 hours, finishing the reaction, purifying and washing to obtain amino epoxy resin;
s2, heating the obtained amino epoxy resin to 60-100 ℃, mixing N, N-dimethylbenzylamine, hydroquinone and acrylic acid, then dripping the mixture into the amino epoxy resin for 20-50min, heating to 90-120 ℃ for continuous reaction, detecting an acid value at regular time, and stopping until the acid value is 3-7 mgKOH/g, thus obtaining the unsaturated vinyl ester polyester resin.
3. The corrosion resistant high strength silane modified polyester resin of claim 2, wherein: in S1, according to parts by weight, 18-20 parts of epoxy resin, 10-20 parts of p-aminophenol, 60-80 parts of epichlorohydrin and 1-2 parts of benzyl triethyl ammonium chloride.
4. The corrosion resistant high strength silane modified polyester resin of claim 2, wherein: in S2, 18-20 parts of amino epoxy resin, 0.5-2 parts of N-N dimethyl benzyl amine, 0.1-0.2 part of hydroquinone and 60-80 parts of acrylic acid.
5. The corrosion resistant, high strength silane modified polyester resin of claim 1, wherein: the preparation of the titanium-containing organic resin comprises the following steps:
adding butyl titanate into dimethylbenzene to prepare a solution, mixing dimethyl diethoxy silane, mono-phenyl triethoxy silane, hydrochloric acid and absolute ethyl alcohol, heating to 50-70 ℃, dropwise adding deionized water, hydrolyzing, preserving heat for 1-4 h, adding the prepared butyl titanate dimethylbenzene solution, dropwise adding deionized water, preserving heat for 1-4 h, performing rotary evaporation, removing ethanol and dimethylbenzene, heating to 100-140 ℃, and preserving heat for 0.5-3 h.
6. The corrosion resistant, high strength silane modified polyester resin of claim 5, wherein: 8-15 parts of dimethyl diethoxy silane, 25-35 parts of monophenyl triethoxy silane, 0.1-1 part of hydrochloric acid and 15-25 parts of butyl titanate.
7. The corrosion resistant, high strength silane modified polyester resin of claim 1, wherein: the preparation method of the tributyltin trilaurate comprises the following steps:
firstly drying monobutyl tin oxide, heating lauric acid to 70-100 ℃, adding the dried monobutyl tin oxide to react for 2-5 h at 60-90 ℃, heating to 80-100 ℃, and preserving heat for 2-5 h to obtain the tributyltin trilaurate.
8. The corrosion resistant, high strength silane modified polyester resin of claim 7, wherein: 50-70 parts of lauric acid and 8-18 parts of monobutyl tin oxide.
9. The corrosion-resistant high-strength silane-modified polyester resin according to any one of claims 1 to 8, wherein: the steps of the silane modified polyester resin are as follows:
mixing unsaturated vinyl ester polyester resin, titanium-containing organic silicon resin and tributyltin trilaurate catalyst, introducing nitrogen, heating to 160-200 ℃, preserving heat for 1-2h, slowly heating to 160-200 ℃, preserving heat for 2-4h, stirring for 10-40 min under vacuum condition, cooling and discharging to obtain the silane modified polyester resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310802354.7A CN116675863B (en) | 2023-07-03 | 2023-07-03 | Corrosion-resistant high-strength silane modified polyester resin and processing technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310802354.7A CN116675863B (en) | 2023-07-03 | 2023-07-03 | Corrosion-resistant high-strength silane modified polyester resin and processing technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116675863A true CN116675863A (en) | 2023-09-01 |
| CN116675863B CN116675863B (en) | 2024-08-09 |
Family
ID=87787379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310802354.7A Active CN116675863B (en) | 2023-07-03 | 2023-07-03 | Corrosion-resistant high-strength silane modified polyester resin and processing technology thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116675863B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004075931A (en) * | 2002-08-21 | 2004-03-11 | Showa Highpolymer Co Ltd | Vinyl ester resin, vinyl ester resin composition and cured product thereof |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
-
2023
- 2023-07-03 CN CN202310802354.7A patent/CN116675863B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004075931A (en) * | 2002-08-21 | 2004-03-11 | Showa Highpolymer Co Ltd | Vinyl ester resin, vinyl ester resin composition and cured product thereof |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 侯红霞: "含钛有机硅改性聚酯及在耐高温防腐涂料中的应用研究", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑, no. 11, 16 October 2011 (2011-10-16), pages 018 - 6 * |
| 张学敏等: "涂料与涂装技术", 31 January 2006, 化学工业出版社, pages: 517 - 518 * |
| 贺曼罗: "环氧树脂胶粘剂", 30 April 2004, 中国石化出版社, pages: 25 - 26 * |
| 陆龙: "单丁基有机锡的合成及对PVC热稳定性的研究", 中国优秀博硕士学位论文全文数据库 (硕士) 工程科技Ⅰ辑, no. 4, 16 March 2007 (2007-03-16), pages 016 - 66 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116675863B (en) | 2024-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108250347B (en) | Salt-fog-resistant phosphate modified acrylic core-shell emulsion | |
| CN110330862A (en) | A kind of low-surface-energy water corrosion-resistant epoxy paint and its preparation and application | |
| CN106118149B (en) | A kind of aqueous inorganic zinc-enriched coating and preparation method thereof | |
| CN101696263A (en) | Epoxy resin curing agent, method for preparing same and application thereof | |
| CN113912840B (en) | Preparation method and application of hollow glass bead modified polyaspartic acid ester | |
| CN106906462A (en) | A kind of metal surface pretreating reagent and preparation method thereof, application | |
| CN109517516A (en) | A kind of cerium bentonite modified watersoluble polyurethane paint and preparation method thereof | |
| CN116987427A (en) | Water-based acrylic resin coating for building and preparation method thereof | |
| CN110591500B (en) | Hyperbranched polysiloxane-containing antifriction, antiwear and flame-retardant epoxy bonding solid lubricating material and preparation and use methods thereof | |
| CN106894009B (en) | A kind of epoxy group POSS modified metal surface pretreating reagent and preparation method thereof, application | |
| CN116675863B (en) | Corrosion-resistant high-strength silane modified polyester resin and processing technology thereof | |
| CN106835093A (en) | A kind of Q types POSS modified metal surface pretreating reagent and preparation method thereof, application | |
| CN112625532B (en) | Efficient anticorrosive water-based acrylic coating and preparation method thereof | |
| CN111303727B (en) | Solvent-free super-thick-paste organic-inorganic hybrid nano modified heavy-duty anticorrosive paint and preparation method thereof | |
| CN110484042B (en) | Self-repairing super-hydrophobic nano anticorrosive coating and preparation method thereof | |
| CN115477893B (en) | Preparation method of water-based alkyd anticorrosive paint | |
| CN111500018A (en) | SiO2 modified fluorinated epoxy resin super-hydrophobic material and preparation method thereof | |
| CN110003762A (en) | A kind of preparation method of high tenacity intensity cathode electrodip painting coating | |
| CN108250950B (en) | Hydrophilic high-corrosion-resistance steel surface silanization treating agent and synthetic method thereof | |
| CN112961350B (en) | High-temperature-resistant resin, preparation method and application thereof, high-temperature-resistant coating containing high-temperature-resistant resin, preparation method and coating | |
| CN102732121B (en) | Composition for water-based glass bottle baking varnish | |
| CN115895379A (en) | Heat-resistant alkali-corrosion-resistant castor oil modified emulsion and preparation method thereof | |
| CN109535864A (en) | White fluorine carbon finishing paint | |
| CN112940614B (en) | Film forming material for high-temperature superheated steam resistant coating and preparation method of coating | |
| CN111019517B (en) | Water-based ceramic coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Country or region after: China Address after: 223100 No. 68, Hongyan Road, salt chemical industry development zone, Hongze District, Huai'an City, Jiangsu Province Applicant after: Jiangsu Bade Polyurethane Co.,Ltd. Address before: 223100 No. 68, Hongyan Road, salt chemical industry development zone, Hongze District, Huai'an City, Jiangsu Province Applicant before: HUAIAN BUD POLYURETHANE SCIENCE & TECHNOLOGY Co.,Ltd. Country or region before: China |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |