WO2023231060A1 - Résine de silicone modifiée par polyester à base aqueuse, procédé de préparation s'y rapportant et son application - Google Patents

Résine de silicone modifiée par polyester à base aqueuse, procédé de préparation s'y rapportant et son application Download PDF

Info

Publication number
WO2023231060A1
WO2023231060A1 PCT/CN2022/097612 CN2022097612W WO2023231060A1 WO 2023231060 A1 WO2023231060 A1 WO 2023231060A1 CN 2022097612 W CN2022097612 W CN 2022097612W WO 2023231060 A1 WO2023231060 A1 WO 2023231060A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
modified silicone
silicone resin
based polyester
acid
Prior art date
Application number
PCT/CN2022/097612
Other languages
English (en)
Chinese (zh)
Inventor
王锡铭
史海兵
Original Assignee
浙江鹏孚隆新材料有限公司
浙江鹏孚隆科技股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 浙江鹏孚隆新材料有限公司, 浙江鹏孚隆科技股份有限公司 filed Critical 浙江鹏孚隆新材料有限公司
Publication of WO2023231060A1 publication Critical patent/WO2023231060A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

Definitions

  • the invention relates to a silicone polymer, in particular to a water-based polyester modified silicone resin, a preparation method and its application, and belongs to the technical field of polymer synthesis.
  • Silicone resin is a semi-inorganic polymer with a highly cross-linked structure. Its special composition and molecular structure make it have the dual characteristics of organic resin and inorganic materials. It is resistant to high temperatures, moisture, water, rust, cold, and weather. , excellent electrical insulation properties and other characteristics, but it has been widely used.
  • current liquid silicone resins are still mainly oily solutions, which brings greater environmental pollution pressure to material applications.
  • Some companies have begun to develop water-based silicone resins, which are mainly divided into two technical routes.
  • the present invention mainly provides a water-based silicone resin technology and provides solutions for the green application of silicone resin.
  • Patent CN106220838 discloses a hydrophobic and heat-resistant silicone-modified polyester resin and its preparation method.
  • the silicone-modified polyester resin described in the patent is a polyol, polybasic acid, and organic silicon intermediate under solvent and catalyst conditions. Obtained by polymerization, the product is a polyester-modified silicone resin solution with high solvent content, which is not conducive to environmental protection.
  • Patent CN104726021 discloses a modified resin aqueous dispersion.
  • the modified resin dispersion described in the patent is polysiloxane-modified polyester resin.
  • the water-based effect is achieved by adding a surfactant containing polyvinyl alcohol.
  • the resin dispersion The medium dispersed particle size ranges from 300 to 1500nm. Since the emulsification effect is supported by the externally added polyvinyl alcohol surfactant, and the dispersed particles in the dispersion have a large size and a wide distribution, the stability period of the dispersion is subject to certain limitations and the stability period is short.
  • the object of the present invention is to provide a water-based polyester modified silicone resin, which has the characteristics of good water-based self-emulsifying performance, high molecular structure stability in the water phase, and good high-temperature resistance of the material. , can be widely used in high-temperature resistant coating fields, such as high-temperature pipeline anti-corrosion, cookware or small household appliance coatings.
  • a kind of water-based polyester modified silicone resin has the following general structural formula:
  • R 1 is selected from methylene or benzylidene
  • R 2 is selected from ethylene, propylene, phenylene or 2,5-dimethyl-1,4-phenyl,
  • x is a positive integer from 5 to 30;
  • M is a hydroxyl-terminated polyester-modified silicone formed by the condensation of a hydroxyl-terminated polyester and an organic silicone intermediate, and the terminal hydroxyl group is an alkyl hydroxyl group.
  • the organic silicone intermediate has a silanol or alkoxy active group.
  • the present invention performs an esterification reaction on the condensation product of a traditional alkyl hydroxyl-terminated polyester and an organic silicone intermediate to convert the alkyl hydroxyl end group into a phenolic hydroxyl end group structure, and at the same time obtains the alkyl hydroxyl end group polyester. Hydrolytic stability, and high Mannich reactivity of phenolic hydroxyl end groups. On the basis of the phenolic hydroxyl compound, Mannich reaction is further performed to obtain a water-based polyester-modified silicone resin with an amine-terminated structure.
  • the molecular weight of the silicone intermediate is 700-5000; the molecular weight of the hydroxyl-terminated polyester is 800-5000, and the average terminal hydroxyl functionality is 2-10.
  • the proportion of phenyl groups in the side groups of the organosilicon intermediate is not less than 50%. Further, the proportion of phenyl groups in the side groups of the organosilicon intermediate is 80%-100%.
  • the polymerization reaction time is usually 1 to 4 hours.
  • the polybasic acid is selected from one or more of terephthalic acid, isophthalic acid, 2-methyl-1,4-phthalic acid, and 1,4-cyclohexanedicarboxylic acid;
  • the alkyl polyol is selected from one or more of neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol.
  • the relative molecular mass ratio of the silanol or alkoxy active group of the organosilicon intermediate to the organosilicon intermediate is 0.01 to 0.1.
  • the ratio of the amine end group R 2 -NH 2 of the water-based polyester modified silicone resin to the amount of the water-based polyester modified silicone resin is x,
  • the water-based polyester modified silicone resin is acidified to form an ammonium salt, and then mixed with an appropriate amount of water to form a self-emulsifying dispersion;
  • the water-based polyester modified silicone resin When x is 10 to 30, the water-based polyester modified silicone resin is mixed with an appropriate amount of water to form a self-emulsifying dispersion.
  • the water-based polyester-modified silicone resin exhibits different water-based effects depending on the amine end group content, and the two emulsified dispersions obtained have good storage stability.
  • the present invention is prepared by the following materials and reaction conditions.
  • each step is carried out under dynamic stirring.
  • each step is carried out under the protection of inert gases such as nitrogen.
  • the hydroxyl-terminated polyester can be a commercially available hydroxyl-terminated polyester with an alkyl hydroxyl end group, or it can be independently synthesized. To facilitate the distinction, an independent synthesis scheme is used in this description.
  • the hydroxyl-terminated polyester is produced by polycondensation of polyol and polybasic acid, wherein the polyol is an alkyl polyol.
  • the water-based polyester modified silicone resin is made of the following raw materials by weight:
  • hydroxyl-terminated polyester 100 parts of hydroxyl-terminated polyester, 50 to 200 parts of silicone intermediate, 0.5 to 2 parts of catalyst, 10 to 50 parts of p-hydroxybenzoic acid, 10 to 40 parts of aldehyde, 8 to 40 parts of diamine, and 50 to 100 parts of solvent;
  • the aldehyde is selected from benzaldehyde, paraformaldehyde, trimerformaldehyde or a mixture of one or more of formaldehyde, preferably benzaldehyde or paraformaldehyde;
  • the diamine is selected from one or more mixtures of ethylenediamine, propylenediamine, butylenediamine, phenylenediamine, xylylenediamine, phenylenediethylamine or 3-methylamine phenylethylamine, preferably ethylenediamine.
  • the solvent is selected from one or a mixture of one or more of cyclopentanol, ethylene glycol or ethylene glycol monoethyl ether, preferably ethylene glycol monoethyl ether.
  • a phthalate catalyst can be selected, preferably one of tetraethyl titanate, tetrabutyl titanate, and butyltin dilaurate. Or a mixture of several. Tetrabutyl titanate is more preferred.
  • the amount of catalyst used is 0.5 to 2% by weight of the organic silicon intermediate.
  • Silicone intermediate used in the synthesis of the polyester modified silicone resin R is selected from H, CH 3 and C 2 H 5 .
  • Silicone intermediates can be commercial silicone intermediates, such as those from Wacker SY231 ⁇ SY300, IC232 ⁇ SIC368, IC678 ⁇ IC836, Shin-Etsu's KR211, KR212, KR214, KR216, Dow Corning's RSN-6018, RSN-3037, RSN-3074, RSN-0233, RSN-0249, Dow's DOWSIL TM RSN-0217, DOWSIL TM RSN-0220 , DOWSIL TM RSN-0233, DOWSIL TM RSN-0249, DOWSIL TM RSN-0255, DOWSIL TM RSN-6018, one or more mixtures.
  • a method for preparing the water-based polyester modified silicone resin which method includes the following steps:
  • the mass ratio of hydroxyl-terminated polyester and silicone intermediate is 0.5-2:1; preferably 0.8-1.5:1, more preferably 1-1.2:1;
  • the mass ratio of polyester modified silicone to p-hydroxybenzoic acid is 1:5 ⁇ 25;
  • the reaction route diagram of the preparation method of the water-based polyester modified silicone resin is:
  • the para-hydroxybenzoic acid used to synthesize compound A is preferably pulverized para-hydroxybenzoic acid powder.
  • the compound A has Structural characteristics, y is a positive integer from 5 to 30.
  • the mass ratio of hydroxyl-terminated polyester and silicone intermediate is 1:1-1.5
  • the mass ratio of polyester-modified silicone and p-hydroxybenzoic acid is 1:10-15
  • m (compound A): m (ethylene glycol monoethyl ether) 10: 1 to 4.
  • the synthesis of the hydroxyl-terminated polyester adopts the following method: polybasic acid and glycol are reacted at 150-200°C for 0.5-1.5 hours, then trihydric alcohol or tetrahydric alcohol is added, and the reaction is continued for 1-2 hours, and then the temperature is raised React at 200-230°C for 2-3 hours, and obtain multi-functional hydroxyl-terminated polyester after dehydration and condensation.
  • the dihydric alcohol, trihydric alcohol or tetrahydric alcohol is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, butylene glycol, butanetriol, neopentyl glycol, pentatriol, pentaerythritol, trihydroxyl
  • ethylene glycol, glycerol, neopentyl glycol, pentaerythritol, trimethylolpropane One or more combinations of trimethylolethane, more preferably one or more combinations of neopentyl glycol, trimethylolpropane, trimethylolethane, and pentaerythritol;
  • the polybasic acid is selected from terephthalic acid, isophthalic acid, terephthalic acid, isophthalic acid, 2-methyl-1,4-phthalic acid, trimellitic anhydride, pyromellitic anhydride, 2,5-di One or a combination of methyl-1,4-phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and 1,4-cyclohexanedicarboxylic acid; preferably p-benzene In dicarboxylic acid, isophthalic acid, 2-methyl-1,4-phthalic acid, trimellitic anhydride, 2,5-dimethyl-1,4-phthalic acid, 1,4-cyclohexanedicarboxylic acid One or a combination of several, more preferably terephthalic acid, isophthalic acid, 2-methyl-1,4-phenylene dicarboxylic acid, 2,5-dimethyl-1,4-phenylene dicarboxylic acid One or a combination of for
  • the water-based polyester-modified silicone resin is mixed with water to form a self-emulsifying dispersion, or is acidified to form a salt and then mixed with water to form a water-based polyester-modified silicone resin self-emulsifying dispersion; the obtained self-emulsifying dispersion Mix with necessary cross-linking agents, pigments, fillers and functional additives to prepare low VOC hot water resistant silicone coatings.
  • the self-emulsifying dispersion replaces the external emulsified oily silicone resin emulsion raw material of water-based silicone coatings in the prior art.
  • the acid used for acidification is selected from one or both of formic acid or phosphoric acid, with phosphoric acid being preferred.
  • Low VOC hot water resistant silicone coating made of water-based polyester modified silicone resin, sprayed and baked at high temperature to form a film, the high temperature resistant silicone coating is obtained.
  • the technical difficulty of the present invention lies in: reasonable selection and proportioning of raw materials so that the resin can obtain the performance characteristics of self-emulsification, hydrolysis resistance, and high temperature resistance. Compared with the prior art, the advantages of the present invention are:
  • the water-based polyester modified silicone resin of the present invention can be used to make high-temperature-resistant water-based silicone coatings instead of existing oil-based silicone resins, greatly reducing the safety of production, storage, and use of silicone coatings and reducing solvent emissions.
  • the water-based polyester modified silicone resin of the present invention improves the hydrolysis resistance of the resin through the selection of synthetic monomers of the polyester resin;
  • the water-based polyester modified silicone resin of the present invention can flexibly control the water dispersion of the resin by regulating the content of amine end groups.
  • the amine end groups introduced by Mannich reaction have the advantages of stable structure and high group content.
  • the resin produced is easier to be water-based, and the final product's water-based self-emulsifying dispersion has higher storage stability.
  • Figure 1 is a scanning electron microscope image of water-based polyester modified silicone resin dispersion particles
  • Figure 2 is a scanning diagram of the particle size of the water-based polyester modified silicone resin emulsion dispersion.
  • Silicone intermediate Dow Corning RSN0217; Wacker IC836.
  • Comparative Examples 1 to 3 used hydroquinone as the polyol in the formula to analyze the impact of containing a large amount of phenol ⁇ H in the polyester chain segment.
  • the test data (Table 3) shows that the phenolic hydroxyl groups in the polyester chain segment will Consumes aldehydes and diamines, thereby affecting the water-based effect of the resin.
  • Examples 1 to 6 are used to investigate: 1. The material ratio of the functional groups n(-OH)/n(-COOH) of alkyl polyols and polybasic acids, and the water-based self-emulsifying performance of water-based polyester modified silicone resin. 2. The influence of the material ratio of alkyl polyol and polybasic acid n (polyol)/n (polyacid) on the water-based self-emulsifying performance of water-based polyester modified silicone resin.
  • the synthetic raw material components and proportions of water-based polyester modified silicone resin are shown in Table 2. After the hydroxyl-terminated polyester synthesis reaction is completed, the materials can be directly added in proportion, or the reaction can be stopped and the hydroxyl-terminated polyester is encapsulated. According to the reaction plan, an appropriate amount of hydroxyl-terminated polyester is taken for the next reaction.
  • the synthesis method of water-based polyester modified silicone resin is:
  • the amine end group content of the water-based polyester-modified silicone resin synthesized in the embodiment is too low to be directly dispersed in water, it can be acidified into a salt in advance and then dispersed in water to maintain the water-based polyester modification in the self-emulsifying dispersion.
  • the solid content of silicone resin is 40%.
  • the ratio of the amine end group R 2 -NH 2 of the water-based polyester modified silicone resin to the amount of the water-based polyester modified silicone resin is x, where the amount of the water-based polyester modified silicone resin is The amount is calculated by the light scattering method.
  • the amount of the amine end group R 2 -NH 2 of the water-based polyester modified silicone resin is the amount of the diamine (ethylenediamine, phenylenediamine) in the raw material. .
  • Example 8 Take the water-based polyester modified silicone resin prepared in Example 8 and configure it into a self-emulsifying dispersion of water-based polyester modified silicone resin with a solid content of 40% according to the above method.
  • 1 Add water and dilute to a solid content of 0.1%. Take A drop of liquid was dropped onto the aluminum foil, vacuum dried, and then a scanning electron microscope analysis was performed on the material. The results are shown in Figure 1. Drying conditions: vacuum degree 0.085MPa, temperature 25°C, cycle 24h. 2The self-emulsifying dispersion with a solid content of 40% was used to detect the particle size of the dispersed particles on a laser particle size analyzer. The results are shown in Figure 2.
  • the water-based polyester-modified silicone resin prepared in Table 2 was prepared into 500g of self-emulsifying dispersion of water-based polyester-modified silicone resin with a solid content of 40% according to the proportions shown in Table 3.
  • the water-based polyester-modified silicone resin was loaded into a transparent container with a diameter of 10 cm.
  • the storage resistance of the dispersion was analyzed in PET plastic bottles, and the results are shown in Table 3.
  • Storage resistance performance analysis method store at 23°C and observe the settlement and stratification every 10 days. If 1/3 of the height is clear, it is judged as settlement and stratification failure; after 180 days, stir the material in the bottle to determine the material adhesion. , no obvious bonding.
  • the water-based polyester-modified silicone resin aqueous dispersion of the present invention has excellent storage resistance.
  • the use of phenol-containing raw materials during polyester synthesis will affect the access position of the Mannich reaction amine end group, thereby affecting the hydrophilicity of the resin; adding high content of silicone intermediates and solvents will affect the water-based polyester modified silicone resin.
  • the storage stability of the dispersion has a certain impact; the selection of polybasic acids and polyols has a certain impact on the storage stability of the water-based polyester modified silicone resin dispersion.
  • the prepared coating is sprayed on the cast aluminum substrate and baked at 150°C/10min and 280°C/10min to obtain the silicone coating.
  • the coating properties are shown in Table 5.
  • the paint film made by using the water-based polyester modified silicone resin of the present invention has high gloss, good thermal hardness, superior water resistance and solvent resistance, and has the same performance as the paint film made by traditional oil-based silicone paint. Close; the use effect meets the protection and aesthetic requirements of high-temperature scenes such as non-stick pans.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Silicon Polymers (AREA)
  • Paints Or Removers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention relève du domaine technique de la synthèse de polymères et concerne un polymère de silicone, et en particulier une résine de silicone modifiée par polyester à base aqueuse, et un procédé de préparation s'y rapportant et son application. La résine de silicone modifiée par polyester à base aqueuse a la formule générale structurale (1) suivante, R1 étant choisi parmi les groupes méthylène et benzylidène, R2 étant choisi parmi les groupes éthylidène, propylidène, phénylène et 2,5-diméthyl-1,4-phénylène, et x étant un nombre entier positif valant de 5 à 30; M étant une résine de silicone modifiée par polyester à terminaison hydroxyle formée par condensation de polyester à terminaison hydroxyle et d'un intermédiaire silicone, le groupe hydroxyle terminal étant un groupe alkyl hydroxyle et l'intermédiaire silicone ayant un groupe actif silanol ou alcoxy. La résine de silicone modifiée par polyester à base aqueuse a les caractéristiques de bonne performance d'auto-émulsification dans de l'eau, de stabilité de structure moléculaire élevée dans une phase aqueuse et de bonne résistance à haute température d'un matériau, et peut être largement appliquée au domaine des revêtements résistants à haute température, tels que des revêtements anticorrosion de tuyaux à haute température, des revêtements d'ustensiles de cuisson ou des revêtements de petits appareils.
PCT/CN2022/097612 2022-05-30 2022-06-08 Résine de silicone modifiée par polyester à base aqueuse, procédé de préparation s'y rapportant et son application WO2023231060A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210601131.X 2022-05-30
CN202210601131.XA CN114989436B (zh) 2022-05-30 2022-05-30 一种水性聚酯改性有机硅树脂、制备方法及其应用

Publications (1)

Publication Number Publication Date
WO2023231060A1 true WO2023231060A1 (fr) 2023-12-07

Family

ID=83030353

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/097612 WO2023231060A1 (fr) 2022-05-30 2022-06-08 Résine de silicone modifiée par polyester à base aqueuse, procédé de préparation s'y rapportant et son application

Country Status (2)

Country Link
CN (1) CN114989436B (fr)
WO (1) WO2023231060A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115433518A (zh) * 2022-10-06 2022-12-06 浙江鹏孚隆新材料有限公司 用于厨具外涂的耐醇耐碱洗水性环保涂料、制备方法及其在厨具方面的应用
CN116262867A (zh) * 2022-12-30 2023-06-16 杭州吉华高分子材料股份有限公司 一种高热硬度水性聚酯改性有机硅耐高温涂料及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09316185A (ja) * 1996-05-29 1997-12-09 M & S Kenkyu Kaihatsu Kk ポリシロキサン変性ポリエステル樹脂の製造法
US20070083026A1 (en) * 2005-10-11 2007-04-12 General Electric Company Polyarylate-siloxane copolymers
US20120010302A1 (en) * 2010-07-08 2012-01-12 Evonik Goldschmidt Gmbh New Types of Polyester-Modified Organopolysiloxanes
CN103113566A (zh) * 2013-01-31 2013-05-22 华南理工大学 有机硅改性端羟基超支化聚酯树脂及其制备方法与应用
CN104829819A (zh) * 2015-02-13 2015-08-12 浙江鹏孚隆科技有限公司 有机硅改性水性聚酯树脂及其制备方法
CN105482089A (zh) * 2015-12-26 2016-04-13 杭州吉华高分子材料股份有限公司 一种水溶性有机硅改性聚酯树脂及其制备方法与应用
CN113272362A (zh) * 2018-12-21 2021-08-17 美国陶氏有机硅公司 硅酮-聚酯共聚物、包括硅酮-聚酯共聚物的密封剂和相关方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2966159D1 (en) * 1978-08-12 1983-10-20 Bayer Ag Process for the preparation of aqueous combined silicone-polyester resin systems and their use
JP5596490B2 (ja) * 2010-10-14 2014-09-24 三洋化成工業株式会社 ポリエステル樹脂水性分散体の製造方法
CN104262589A (zh) * 2014-09-05 2015-01-07 广州秀珀化工股份有限公司 一种具有Gemini表面活性剂结构的非离子型自乳化水性环氧固化剂及其制备方法
CN104672399B (zh) * 2015-03-13 2020-08-18 北京金汇利应用化工制品有限公司 一种新型水性双组份聚氨酯胶黏剂用丙烯酸改性树脂的制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09316185A (ja) * 1996-05-29 1997-12-09 M & S Kenkyu Kaihatsu Kk ポリシロキサン変性ポリエステル樹脂の製造法
US20070083026A1 (en) * 2005-10-11 2007-04-12 General Electric Company Polyarylate-siloxane copolymers
US20120010302A1 (en) * 2010-07-08 2012-01-12 Evonik Goldschmidt Gmbh New Types of Polyester-Modified Organopolysiloxanes
CN103113566A (zh) * 2013-01-31 2013-05-22 华南理工大学 有机硅改性端羟基超支化聚酯树脂及其制备方法与应用
CN104829819A (zh) * 2015-02-13 2015-08-12 浙江鹏孚隆科技有限公司 有机硅改性水性聚酯树脂及其制备方法
CN105482089A (zh) * 2015-12-26 2016-04-13 杭州吉华高分子材料股份有限公司 一种水溶性有机硅改性聚酯树脂及其制备方法与应用
CN113272362A (zh) * 2018-12-21 2021-08-17 美国陶氏有机硅公司 硅酮-聚酯共聚物、包括硅酮-聚酯共聚物的密封剂和相关方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Mater Thesis", 8 June 2011, SHANDONG UNIVERSITY OF LIGHT INDUSTRY, CN, article WANG, NUANSHENG: "Mannich Reaction of Ethylenediamine with P-Cresol", pages: 1 - 65, XP009551082 *

Also Published As

Publication number Publication date
CN114989436A (zh) 2022-09-02
CN114989436B (zh) 2023-04-28

Similar Documents

Publication Publication Date Title
WO2023231060A1 (fr) Résine de silicone modifiée par polyester à base aqueuse, procédé de préparation s'y rapportant et son application
US7129310B2 (en) Solid siliconized polyester resins for powder coatings
US6893724B2 (en) Silicone-polyester-polysilicate hybrid compositions for thermal resistance coating
AU2013360756B2 (en) A coating composition
CN103492453A (zh) 用于涂料的聚酯粘结树脂以及含有该聚酯粘结树脂的涂料组合物
TW200927810A (en) Inorganically modified polyester binder preparation, processes for production and use thereof
CN103897197B (zh) 有机硅改性聚酯环氧树脂的制备方法
CN106700047A (zh) 一种改性高固低粘的聚酯树脂及其制备方法与在涂料中的应用
CN103160099B (zh) 改性醇酸树脂、其制备方法及双组份底漆
CN111995743B (zh) 一种倍半硅氧烷改性双官能团聚酯树脂及其制备方法
CN112062941A (zh) 一种6040型聚酯树脂及其制备方法
CN115433518A (zh) 用于厨具外涂的耐醇耐碱洗水性环保涂料、制备方法及其在厨具方面的应用
CN112521591B (zh) 一种持久耐高温及硬度优的粉末涂料用聚酯树脂及制备方法
JPS58191765A (ja) 被覆用組成物
CN105061770A (zh) 一种有机氟硅光固化树脂及其制备方法和应用
CN107698749B (zh) 一种poss改性高硬度耐水性醇酸树脂及其制备方法
CN114561001A (zh) 一种高固低黏有机硅改性聚酯树脂及耐高温高固体分涂料
CN114149575A (zh) 一种高流平、持久耐高温型聚酯树脂及其制备方法
WO2022109791A1 (fr) Copolymère de polyester à base d'eau, son procédé de préparation et son application
CN102093808B (zh) 一种化工桶外涂清漆及其制备方法
CN117586296A (zh) 一种用于环氧树脂的固化剂、其制备方法和应用
CN115572376B (zh) 高光泽、高储存稳定性粉末涂料用聚酯树脂及其制备方法
JPH03139581A (ja) 被覆用樹脂組成物及び耐熱性塗料
CN109824879B (zh) 流平性及耐溶剂优良的环氧固化70:30聚酯树脂及制备方法
WO2022120566A1 (fr) Résine de silicone

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22944386

Country of ref document: EP

Kind code of ref document: A1