CN113292730A - Modified organic silicon resin, preparation method thereof and normal-temperature curing coating - Google Patents
Modified organic silicon resin, preparation method thereof and normal-temperature curing coating Download PDFInfo
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- CN113292730A CN113292730A CN202110410234.3A CN202110410234A CN113292730A CN 113292730 A CN113292730 A CN 113292730A CN 202110410234 A CN202110410234 A CN 202110410234A CN 113292730 A CN113292730 A CN 113292730A
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- organic silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The invention relates to a modified organic silicon resin, a preparation method thereof and a normal-temperature curing coating, wherein the preparation method of the modified organic silicon resin comprises the following steps: sequentially adding a silane solvent, hydroxyl-terminated hyperbranched polyester and a catalyst into a reaction kettle, heating to 100-110 ℃, adding a carboxyl-containing organic silicon resin, further heating to 170-180 ℃, carrying out heat preservation reaction for 3-4 hours, and cooling to obtain a modified organic silicon resin; the normal temperature curing coating comprises the following base materials in parts by weight: 30-40 parts of modified organic silicon resin prepared by the preparation method and 20-30 parts of dimethylbenzene; the curing temperature of the coating is 30-40 ℃. The invention adopts hyperbranched polyester containing hydroxyl to modify organic silicon resin containing carboxyl, and can ensure that the obtained modified organic silicon resin has the effect of curing at normal temperature.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to modified organic silicon resin, a preparation method thereof and a normal-temperature curing coating.
Background
The organic silicon resin is combined with other resins in the paint industry, the problems of high price, incapability of self-drying at normal temperature, poor adhesion with common base materials, poor mechanical strength of a coating film at high temperature and the like of the organic silicon resin paint can be mainly solved, and the modified resin has the advantages of two resins and is more suitable for paint application.
The organic silicon resin has excellent performances such as weather resistance, heat resistance, stain resistance, chemical stability and the like, and is increasingly widely applied in various fields. However, pure silicone resins generally require high-temperature curing (above 120 ℃), have long curing time and poor adhesion to substrates, which limits their applications to some extent. Generally, modification of silicone resin is required, and the modification method is classified into a physical method and a chemical method.
The physical method usually adopts a physical blending method, and organic resin and organic silicon resin with good miscibility are physically mixed, although the mixing method is simple, the modification effect is poor. In most cases, the silicone resin and the organic resin are modified by chemical reaction to achieve the modification effect. In general, active groups (such as hydroxyl, unsaturated hydrocarbon groups, etc.) of organic resins are reacted with hydroxyl, alkoxy, unsaturated hydrocarbon groups in suitable organic silicon oligomers through co-condensation, copolymerization, co-addition, etc., to introduce active groups at the end or side groups of the siloxane chains of the organic silicon, and the active groups are combined with other macromolecules to generate block, graft or interpenetrating network copolymers, etc.
Hyperbranched polymers are macromolecules which have small molecular monomers and are grown into three-dimensional structures through polymerization castings, are obviously different from linear macromolecules and cross-linked reticular macromolecule structures, and are applied to many fields due to unique structures. In the prior art, hyperbranched polymers are adopted to modify epoxy resin, so that the epoxy resin has the effects of enhancing and toughening the epoxy resin, but the hyperbranched polymers are adopted to modify organic silicon resin, so that the curing temperature of the modified organic silicon resin is reduced, and the reports are not found.
Disclosure of Invention
In order to solve the technical problem of high curing temperature of the organic silicon resin, the modified organic silicon resin, the preparation method thereof and the normal-temperature curing coating are provided. The hyperbranched polyester modified organic silicon resin is adopted, so that the obtained modified organic silicon resin has the effect of curing at normal temperature.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of modified organic silicon resin comprises the following steps: sequentially adding a silane solvent, hydroxyl-terminated hyperbranched polyester and a catalyst into a reaction kettle, heating to 100-110 ℃, adding a carboxyl-containing organic silicon resin, further heating to 170-180 ℃, carrying out heat preservation reaction for 3-4 hours, and cooling to obtain the modified organic silicon resin.
Furthermore, the hydroxyl number of each mole of the hydroxyl-terminated hyperbranched polyester is 5-15, the hydroxyl value is 400-700 mg KOH/g, and the molecular weight is 500-1500 g/mol.
Further, the content of carboxyl in the organic silicon resin containing carboxyl is 10-20%.
Further, the catalyst is any one of diethyl stannous dioctoate and dibutyl tin trilaurate.
Further, the silane solvent is a mixture of any one of glycidoxypropyltriethoxysilane or glycidoxypropyltrimethoxysilane and aminopropyltriethoxysilane in a mass ratio of (3-4) to (6-7).
Further, the modified organic silicon resin comprises the following components in percentage by mass: 50-60% of hydroxyl-terminated hyperbranched polyester, 15-20% of silane solvent and 25-30% of organic silicon resin containing carboxyl; the dosage of the catalyst is 1-2% of the mass of the organic silicon resin containing carboxyl.
In another aspect, the present invention provides a modified silicone resin prepared by the above-described preparation method.
The last aspect of the invention provides a normal temperature curing coating, which comprises the following base materials in parts by weight: 30-40 parts of modified organic silicon resin prepared by the preparation method and 20-30 parts of dimethylbenzene; the curing temperature of the coating is 30-40 ℃.
Further, the coating also comprises the following fillers in parts by weight: 5-8 parts of kaolin, 5-7 parts of alumina powder, 5-10 parts of wollastonite powder, 8-15 parts of titanium dioxide and 2-5 parts of polyether modified organic silicon flatting agent. The required properties of the coating can be achieved by adding corresponding functional fillers, levelling agents, defoamers, pigments and other additives.
The beneficial technical effects are as follows:
the hyperbranched polyester polyol containing the terminal hydroxyl is adopted to modify the organic silicon resin containing the carboxyl, and the hyperbranched polyester has a highly branched structure and a large number of terminal hydroxyl active groups, so that the modified organic silicon resin obtained after reaction has normal-temperature curing performance, namely the hyperbranched polyester polyol containing the terminal hydroxyl can effectively reduce the curing temperature of the organic silicon resin, and the coating cured at the normal temperature has better performance. The modification method is simple, the raw materials are easy to obtain, the popularization is convenient, the stability of the modified organic silicon resin is higher in use, and the economic benefit is obvious.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
The hydroxyl-terminated hyperbranched polyester used below is HyPer H10 series hydroxyl-terminated hyperbranched polyester of Wuhan hyperbranched resin technology Limited, the hydroxyl number is 5-15, the hydroxyl value is 400-700 mg KOH/g, and the molecular weight is 500-1500 g/mol. The silicone resin containing a carboxyl group is a Dow Corning company product (the molecular structure thereof is mentioned in Dow Corning company patent 201380037545.3). The polyether modified organic silicon leveling agent is a product of Kunshan Louis polymer materials Co.
Example 1
A preparation method of modified organic silicon resin comprises the following steps: adding 5kg of hydroxyl-terminated hyperbranched polyester (the number of hydroxyl groups in each mole is 6), 0.6kg of glycidyl ether oxypropyltriethoxysilane, 1.4kg of aminopropyltriethoxysilane and 0.03kg of diethyl stannous dioctoate into a reaction kettle, heating to 100 ℃, adding 3kg of organic silicon resin with 10 percent of carboxyl group, further heating to 170 ℃, carrying out heat preservation reaction for 3 hours, and cooling to obtain the modified organic silicon resin.
The normal-temperature curing coating comprises 40 parts of modified organic silicon resin prepared in the embodiment, 30 parts of dimethylbenzene, 8 parts of kaolin, 7 parts of alumina powder, 10 parts of wollastonite powder, 15 parts of titanium dioxide and 5 parts of polyether modified organic silicon flatting agent. The above materials were ground in a grinder for 5 hours to obtain the dope.
Example 2
A preparation method of modified organic silicon resin comprises the following steps: adding 6kg of hydroxyl-terminated hyperbranched polyester (the number of hydroxyl groups in each mole is 12, HyPer H102), 0.6kg of glycidyl ether oxypropyltrimethoxysilane, 0.9kg of aminopropyltriethoxysilane and 0.05kg of dibutyltin trilaurate into a reaction kettle, heating to 110 ℃, adding 2.5kg of organic silicon resin with 20 percent of carboxyl content, further heating to 180 ℃, preserving heat for reaction for 4 hours, and cooling to obtain the modified organic silicon resin.
The normal-temperature curing coating comprises 30 parts of modified organic silicon resin prepared in the embodiment, 20 parts of dimethylbenzene, 5 parts of kaolin, 5 parts of alumina powder, 5 parts of wollastonite powder, 8 parts of titanium dioxide and 2 parts of polyether modified organic silicon flatting agent. The above materials were ground in a grinder for 5 hours to obtain the dope.
Example 3
A preparation method of modified organic silicon resin comprises the following steps: adding 5.5kg of hydroxyl-terminated hyperbranched polyester (the number of hydroxyl in each mole is 6, HyPer H101), 0.63kg of glycidyl ether oxypropyltrimethoxysilane, 1.17kg of aminopropyltriethoxysilane and 0.042kg of stannous diethyldioctoate into a reaction kettle, heating to 105 ℃, adding 2.8kg of organic silicon resin with 15% of carboxyl content, further heating to 175 ℃, carrying out heat preservation reaction for 3.5 hours, and cooling to obtain the modified organic silicon resin.
The normal-temperature curing coating comprises 35 parts of modified organic silicon resin prepared in the embodiment, 25 parts of dimethylbenzene, 7 parts of kaolin, 6 parts of alumina, 7 parts of wollastonite powder, 10 parts of titanium dioxide and 3 parts of polyether modified organic silicon flatting agent. The above materials were ground in a grinder for 5 hours to obtain the dope.
Example 4
A preparation method of modified organic silicon resin comprises the following steps: adding 5.5kg of hydroxyl-terminated hyperbranched polyester (the number of hydroxyl groups in each mole is 6, HyPer H101), 0.63kg of glycidyl ether oxypropyltriethoxysilane, 1.17kg of aminopropyltriethoxysilane and 0.042kg of dibutyltin trilaurate into a reaction kettle, heating to 100 ℃, adding 2.8kg of organic silicon resin with 15% of carboxyl content, further heating to 175 ℃, keeping the temperature for reaction for 3.5 hours, and cooling to obtain the modified organic silicon resin.
The normal-temperature curing coating comprises 30 parts of modified organic silicon resin prepared in the embodiment, 30 parts of dimethylbenzene, 7 parts of kaolin, 6 parts of alumina, 7 parts of wollastonite powder, 10 parts of titanium dioxide and 3 parts of polyether modified organic silicon flatting agent. The above materials were ground in a grinder for 5 hours to obtain the dope.
Comparative example 1
This comparative example modified silicone resin was prepared in the same manner as in example 1, except that aminopropyltriethoxysilane was not added and the amount of glycidylethyloxypropyltriethoxysilane added was 2 kg. The preparation of the coating was the same as in example 1.
The coatings of the above examples and comparative examples were applied to tinplate and the cured coatings were tested for their properties, the results of which are shown in Table 1. The hardness measurement method is carried out according to GB/T6739-2006, the adhesion measurement method is carried out according to GB/T9286-1998, and the wear resistance measurement method is carried out according to GB/T1768-2006.
TABLE 1 comparison of coating Cure Properties of examples and comparative examples
As shown in Table 1, the modified organic silicon resin obtained by modifying the organic silicon resin containing carboxyl with the hyperbranched polyester containing hydroxyl by adopting the method disclosed by the invention has the effect of curing at normal temperature after being diluted, and the curing temperature is between 30 and 40 ℃. In comparative example 1, aminopropyltriethoxysilane was not added to the silane solvent, and it can be seen from the curing temperature in Table 1 that the addition of the aminopropyltriethoxysilane solvent in example 1 also lowers the curing temperature. It is inferred that the effect of the present invention to obtain the curing temperature reduction is based on the effect of the combined action of the modified silicone resin obtained by modifying the carboxyl group-containing silicone resin with the hydroxyl group-containing hyperbranched polyester and the aminopropyltriethoxysilane solvent added during the reaction. The principle that the curing temperature can be reduced to 30-40 ℃ by adopting the method is unknown, and possible reasons are as follows: the Si-O bond in the organic silicon resin is high in performance and not easy to open at normal temperature to form crosslinking, and after hyperbranched polyester containing hydroxyl is introduced to the branched chain carboxyl of the organic silicon for reaction, the structure of the formed high molecular compound is easy to crosslink at low temperature, and the high-temperature resistance and other excellent performances of the original organic silicon resin can be maintained after crosslinking.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A preparation method of modified organic silicon resin is characterized by comprising the following steps: sequentially adding a silane solvent, hydroxyl-terminated hyperbranched polyester and a catalyst into a reaction kettle, heating to 100-110 ℃, adding a carboxyl-containing organic silicon resin, further heating to 170-180 ℃, carrying out heat preservation reaction for 3-4 hours, and cooling to obtain the modified organic silicon resin.
2. The method for preparing modified silicone resin according to claim 1, wherein the hydroxyl-terminated hyperbranched polyester contains 5 to 15 hydroxyl groups per mole, a hydroxyl value of 400 to 700mg KOH/g, and a molecular weight of 500 to 1500 g/mol.
3. The method for preparing modified silicone resin according to claim 1, wherein the carboxyl group content in the silicone resin containing carboxyl groups is 10% to 20%.
4. The method for preparing the modified silicone resin according to claim 1, wherein the catalyst is any one of stannous diethyldioctoate and dibutyltin dilaurate.
5. The method of claim 1, wherein the silane solvent is a mixture of glycidoxypropyltriethoxysilane or glycidoxypropyltrimethoxysilane and aminopropyltriethoxysilane at a mass ratio of (3-4) to (6-7).
6. The method for preparing modified silicone resin according to claim 1, wherein the modified silicone resin comprises the following components in percentage by mass: 50-60% of hydroxyl-terminated hyperbranched polyester, 15-20% of silane solvent and 25-30% of organic silicon resin containing carboxyl; the dosage of the catalyst is 1-2% of the mass of the organic silicon resin containing carboxyl.
7. A modified silicone resin produced by the production method according to any one of claims 1 to 6.
8. The normal-temperature curing coating is characterized by comprising the following base materials in parts by weight: 30-40 parts of modified organic silicon resin prepared by the preparation method of any one of claims 1-6, and 20-30 parts of xylene; the curing temperature of the coating is 30-40 ℃.
9. The normal-temperature curing coating as claimed in claim 8, further comprising the following fillers in parts by weight: 5-8 parts of kaolin, 5-7 parts of alumina powder, 5-10 parts of wollastonite powder, 8-15 parts of titanium dioxide and 2-5 parts of polyether modified organic silicon flatting agent.
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| CN202110410234.3A CN113292730A (en) | 2021-04-16 | 2021-04-16 | Modified organic silicon resin, preparation method thereof and normal-temperature curing coating |
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| CN202110410234.3A CN113292730A (en) | 2021-04-16 | 2021-04-16 | Modified organic silicon resin, preparation method thereof and normal-temperature curing coating |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457166A (en) * | 1993-08-10 | 1995-10-10 | Shin-Etsu Chemical Co., Ltd. | Process for preparing a polyester-modified silicone resin and a curable composition comprising the polyester-modified silicone resin |
| CN102504271A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing hyperbranched polyester modified organic silicon resin |
| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
| CN102504265A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing polyester modified organic silicon resin and coating containing the resin |
| CN103113566A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof |
| CN106366916A (en) * | 2016-09-05 | 2017-02-01 | 华南理工大学 | Normal temperature curable epoxy modified organic silicone resin, preparation method thereof and application |
| WO2018001100A1 (en) * | 2016-06-28 | 2018-01-04 | 佛山市珀力玛高新材料有限公司 | Water-soluble organosilicon resin and application thereof |
-
2021
- 2021-04-16 CN CN202110410234.3A patent/CN113292730A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5457166A (en) * | 1993-08-10 | 1995-10-10 | Shin-Etsu Chemical Co., Ltd. | Process for preparing a polyester-modified silicone resin and a curable composition comprising the polyester-modified silicone resin |
| CN102504271A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing hyperbranched polyester modified organic silicon resin |
| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
| CN102504265A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Method for preparing polyester modified organic silicon resin and coating containing the resin |
| CN103113566A (en) * | 2013-01-31 | 2013-05-22 | 华南理工大学 | Organic silicon modified hydroxyl-terminated hyperbranched polyester resin, and preparation method and application thereof |
| WO2018001100A1 (en) * | 2016-06-28 | 2018-01-04 | 佛山市珀力玛高新材料有限公司 | Water-soluble organosilicon resin and application thereof |
| CN106366916A (en) * | 2016-09-05 | 2017-02-01 | 华南理工大学 | Normal temperature curable epoxy modified organic silicone resin, preparation method thereof and application |
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Application publication date: 20210824 |