Method of surface modification of polyester composites with organosilicon compounds

Abstract

The subject of the invention is a method of modifying the surface of polyester composites with organosilicon compounds obtained by a hydrosilylation reaction. The invention is characterized by the fact that polyhydrosiloxane (PHS) and toluene are placed in a reaction vessel and mixed, after which a composition of olefins is added to the resulting mixture: allyl methacrylate and a compound selected from 2,2,2,3,3,4,4,5,5- octafluoropentyl allyl ether (OFP), octene (OCT), octadecene (OD), perfluorohexene (F- HEX), perfluorooctene (F- OCT) or perfluorodecene (F-DEC), and a catalyst is added, after which the resulting mixture is heated and stirred, and then the solvent is evaporated, after which it is dissolved in a selected organic solvent to form a modifier solution, which is then applied to the surface of the polyester composite, after which the polyester composite is heated.

Description

DESCRIPTIONTitle of the InventionMETHOD OF SURFACE MODIFICATION OF POLYESTER COMPOSITES WITH ORGANOSILICON COMPOUNDSTechnical Field

[0001] This invention focuses on a method for modifying the surface of polyester composites using organosilicon compounds obtained through hydrosilylation reactions. The method is characterized by the fact that the application of functionalized polysiloxanes occurs directly on the surface of the polyester composite, which leads to a change in the hydrophobic properties of the materials.Background Art

[0002] Various ways of modifying polyester composites are known, such as those presented in Japanese patent JP3534943B2, which describes a way to produce a polyester resin modified with polysiloxane without causing a decrease in molecular weight. 1 mol of a linear polyester resin containing dicarboxylic acid component units and dihydroxy component units is reacted with 0.001-0.05 mol of diaminopolysiloxane.

[0003] Japanese patent application JP2008138055A, on the other hand, shows a thermoplastic resin composition is obtained by mixing (A) 30-50% by weight of a thermoplastic polyester resin, (B) 0.01-1% by weight of a specific polysiloxane, (C) 0.01- 1% by weight of a fatty acid ester, (D) 1-10% by weight of a brominated epoxy compound, and (F) 10-40% by weight of an antimony compound under a glass fiber, fatty acid ester, (D) 5 -20% by weight of a brominated epoxy compound, (E) 1-10% by weight of an antimony compound and (F) 10-40% by weight of a glass fiber, provided that the sum of components (A) through (F) is 100% by weight.

[0004] Conversely, Chinese patent CN111995743B describes the manufacture of a bifunctional silsesquioxane-modified polyester resin. The invention discloses a bifunctional polyester resin modified with silsesquioxane, which is obtained by polycondensation in the melt phase of the following raw materials (by weight): 20.0 to55.0 percent silsesquioxane, 25.0 to 40.0 percent polyhydric alcohol, 25.0 to 50.0 percent polyatomic acid, 4.0 to 18.0 percent acidolytic agent, 0.03 to 0.12 percent catalyst and 0.01 to 0.4 percent curing accelerator.

[0005] On the other hand, Chinese patent application CN103113812A describes a polyester powder coating modified with a POSS (polyhedral oligomeric silsesquioxane) based nanomaterial and a method of manufacturing it.

[0006] In contrast, Japanese patent JP4566592B2 describes a polyester resin additive that contains silsesquioxane. The polyester resin composition contains polyester resin and silsesquioxane. A method of manufacturing a polyester resin composition includes a step of mixing a polyester resin and a silsesquioxane at a melting temperature (Tm) of the polyester resin or higher and a step of carrying out a heat treatment in a temperature range from the glass transition temperature (Tg) of the polyester resin composition to a temperature lower than Tm.

[0007] Chinese patent application CN105153654A describes a fiber-reinforced polyester composition and a method of making it. POSS (polyhedral oligomeric silsesquioxane) with an active epoxy side group is used as a chain extender and rigid particle curing agent to modify and reinforce PET (polyethylene terephthalate), respectively.

[0008] Japanese patent application JP2004307738A, on the other hand, describes a polyester composition obtained by dispersing a polyhedral oligomeric silsesquioxane (POSS) with an average dispersion diameter of <500 nm in a polyester composed of a bifunctional acid component consisting mainly of a dicarboxylic acid and at least one type of glycol component.

[0009] On the other hand, Japanese patent JP6388308B2 describes a coating composition comprising (a) a polyester resin containing hydroxyl groups having a hydroxyl group number of 10 to 200 mgKOH / g and an acid number of 30 mgKOH / g or less, (b) a crosslinking agent and (c) a specific fluorine-containing polysiloxane with 0.1 to 10 pct. by weight of the fluorine-containing polysiloxane (c) per 100 pct. by weight of the total solids content of the polyester resin containing hydroxyl groups (a) and crosslinking agent (b), and an anionic surfactant (d) with 0.1 to 20 pts. per 100 pts. by weight of the total solids content of the polyester resin containing hydroxyl groups (a) and crosslinking agent (b).

[0010] On the other hand, Chinese patent CN111560186B presents a foaming paint that is prepared by weight from 40-60 parts saturated polyester resin, 5-20 parts hardener, 0- 20 parts solvent and 3-8 parts touch additive and touch aid selected from polysiloxane, fluorine-modified polysiloxane, nanometer calcium carbonate and nanometer magnesium carbonate.Summary of InventionTechnical Problem

[0011] However, the presented solutions do not adhere to the composition outlined in this invention. This deviation may result in insufficient hydrophobicity in the final products, leading to water and contaminant accumulation, ultimately damaging their surfaces and diminishing their quality and aesthetics. In addition, the application of functionalized polysiloxanes directly to the surface of the polyester composite is unknown, which may prolong the modification process and limit the ability to control the process and increase the cost of the final product.

[0012] The purpose of the invention was to develop such a method of modifying the surface of polyester composites with organosilicon compounds, which will allow the use of organosilicon modifiers for surface modification of polyester composites, leading to changes in the hydrophobic properties of the materials. Functionalized polysiloxanes are applied directly to the surface of the polyester composite. The method, as per the invention, addresses the aforementioned issues associated with an insufficiently high degree of hydrophobicity of the materials, which can cause deposition of water, its compounds and impurities on the materials, which in turn can damage their surface and / or deteriorate its properties and visual qualities. In addition, the method accelerates the modification of polyester composites by applying functionalized polysiloxanes directly to the material surface.Solution to Problem

[0013] The core of the invention lies in a method for modifying the surface of polyester composites with organosilicon compounds. The invention is characterized by the fact that: polyhydrosiloxane (PHS) and toluene are placed in a reaction vessel and mixed, after which a composition of olefins is added to the resulting mixture: allyl methacrylate and a compound selected from: allyl ether 2, 2, 2, 3, 3,4,4,5,5-octafluoropentyl (OFP), octene (OCT), octadecene (OD), perfluorohexene (F-HEX), perfluorooctene (F-OCT) or perfluorodecene (F-DEC), and a catalyst is added, after which the resulting mixture is heated and stirred, and then the solvent is evaporated, after which it is dissolved in a selected organic solvent to form a modifier solution, which is then applied to the surface of the polyester composite, after which the polyester composite is heated.

[0014] It is favorable when the ratio of polyhydrosiloxane (PHS) to toluene is from 1:10 to 1:20.

[0015] Advantageously, the ratio of allyl methacrylate to the selected compound from the olefin group is from 1:4 to 4:1.

[0016] It is good if the catalyst is a catalyst that is a platinum(O) complex.

[0017] It is advantageous to heat the resulting mixture in the range of 60 to 110°C and stir it for at least 24 hours. Simultaneously, the polyester composite should be heated at 100°C for a minimum of 4 hours.

[0018] It is good if the chosen organic solvent for the preparation of the modifier solution for application to the surface of the composite is isopropyl alcohol, and the mixture is dissolved in it in a ratio of 1:10 to 1:30.

[0019] Advantageously, the method of applying the mixture to the surface of the polyester composite includes spraying.Advantageous Effects of Invention

[0020] The positive outcomes of the method for modifying the surface of polyester composites with organosilicon compounds, as per the invention, include an increased contact angle for the modified composites, heightened hydrophobicity of the modified surfaces, and prevention of water accumulation and deposits on the manufacturedproduct's surface. These materials can find application in areas where high resistance to moisture and dirt is required, or in the production of protective coatings. This offers new opportunities for the use of polyester composites in various industrial fields. It is also beneficial to facilitate and speed up the process of modifying the surface of polyester composites by directly applying functionalized polysiloxanes to the surface of the material.Description of Embodiments

[0021] In the example implementation, the method of surface modification of polyester composites with organosilicon compounds includes the following steps:• polyhydrosiloxane (PHS) and toluene are placed in a reaction vessel and mixed, with a ratio of PHS to toluene of 1:10. In another example of implementation, the ratio is 1:20, followed by addition to the resulting mixture• a composition of olefins: allyl methacrylate and allyl 2, 2, 2, 3, 3, 4, 4, 5, 5- octafluoropentyl ether (OFP) (2), the ratio of the composition of allyl methacrylate and OFP is 1:1. In another example of implementation, the ratio is 2:1, and then• catalyst is added, in the example implementation the catalyst being a platinum(O) complex, followed by• the resulting mixture is heated to 60° C and stirred with a magnetic stirrer for 48 hours. In another realization example, the mixture was heated to 1100C and stirred for 24 hours. Subsequently, the solvent was evaporated to obtain poly((2,2,3,3,4,4,5,5-octafluoropentoxy)propyl)methyl)methylsiloxane) modifier, terminated with trimethoxysilyl groups, and then• the modifier is dissolved in an organic solvent of choice, in the implementation example in isopropyl alcohol, in a ratio of 1:10. In this implementation example, 10 g of the mixture and 100 g of isopropyl alcohol were used. Another example employed a ratio of 1:19, using 10 g of the mixture and 190 g of isopropyl alcohol. In a different example, a ratio of 1:30, with 10 g of the mixture and 300 g of isopropyl alcohol is used, and the resulting solution is applied to the surface of the polyester composite by spraying, then• the polyester composite with a layer of modifier applied is heated in an oven at a temperature of 100° C for 4 hours. In another example of implementation, heating of the polyester composite was realized for 6 hours.The course of the reaction is shown in Formula (1). Formulas (2) show the structural formulas of selected compounds from the olefin group.

[0022] In the next implementation example, octene (OCT) (2) was used as the chosen compound from the olefin group, and the ratio of allyl methacrylate to OCT is 4:1. Thus, a solution of the compound poly((octyl)methylsiloxane)-co-(propylmethacrylate)- methylsiloxane), terminated with trimethoxysilyl groups, was produced.

[0023] In the following implementation example, octadecene (OD) (2) was used as the chosen compound from the olefin group, and the ratio of allyl methacrylate to OD is 1:1. In another example, the ratio of allyl methacrylate to OD of 1:4 was used. In this way, a solution of the compound poly((octadecyl)methylsiloxane)-co(propylmethacrylate)- methylsiloxane), terminated with trimethoxysilyl groups, was produced.

[0024] In another implementation example, perfluorohexene (F-HEX) (2) was used as the chosen compound from the olefin group, and the ratio of allyl methacrylate to F-HEX is 1:1. In another example, a ratio of allyl methacrylate to F-HEX of 1:4 was used. Thus, a solution of the compound poly((perfluorohexyl)methylsiloxane)-co-(propylmethacrylo)- methylsiloxane), terminated with trimethoxysilyl groups, was produced.

[0025] In the next example of implementation, perfluorooctene (F-OCT) (2) was used as the chosen compound from the olefin group, and the ratio of allyl methacrylate to F-OCTis 1:1. In another example, a ratio of allyl methacrylate to F-OCT of 1:4 was used, and a solution of the compound poly((perfluorooctyl)methylsiloxane)-co(propylmethacrylo)- methylsiloxane), terminated with trimethoxysilyl groups, was produced.

[0026] In another example of implementation, perfluorodecene (F-DEC) (2) was used as the chosen compound from the olefin group, and the ratio of allyl methacrylate to F-DEC is 1:1. In another example, a ratio of allyl methacrylate to F-DEC of 1:2 was used. Thus, a solution of the compound poly((perfluorodecyl)methylsiloxane)-co-(propylmethacrylo)- methylsiloxane), terminated with trimethoxysilyl groups, was produced.

[0027] The application of a solution of the mentioned compounds to the surface of polyester composites was performed once. In another example of implementation, the application was carried out twice. In another example, the application was carried out three times.

[0028] The study revealed that the values of the wetting angles of the produced coatings on the surface of the polyester composites were in the range of 99° to 111°, indicating their significant hydrophobicity.

Claims

Patent claims1. A method of modifying the surface of polyester composites with organosilicon compounds, characterized in that:• polyhydrosiloxane (PHS) and toluene are placed in a reaction vessel and mixed, followed by• to the resulting mixture is added composition of olefins: allyl methacrylate and a compound selected from 2, 2, 2, 3, 3, 4, 4, 5, 5- octafluoropentyl allyl ether (OFP), octene (OCT), octadecene (OD), perfluorohexene (F-HEX), perfluorooctene (F-OCT) or perfluorodecene (F-DEC), and then• catalyst is added, after which• the resulting mixture is heated and stirred, and then the solvent is evaporated, after which• it is dissolved in a selected organic solvent to form a modifier solution, which is then applied to the surface of the polyester composite, and then• the polyester composite is heated.

2. Method according to claim 1, characterized in that the ratio of polyhydrosiloxane to toluene is from 1:10 to 1:20.

3. Method according to either claim 1 or 2, characterized in that the ratio of allyl methacrylate to the selected compound from the olefin group is from 1:4 to 4:1.

4. Method according to any of the claims 1 to 3, characterized in that the catalyst is a catalyst constituting a platinum(O) complex.

5. The method according to any of the claims. 1 to 4, characterized in that the resulting mixture is heated to a temperature in the range of 60 to 110° C and stirred for at least 24 hours, the heating of the polyester composite being carried out at 100° C for at least 4 hours.

6. The method according to any of claims 1 to 5, characterized in that the selected organic solvent for the preparation of the modifier solution forapplication to the surface of the composite is isopropyl alcohol, and the mixture is dissolved in it in a ratio of 1:10 to 1:30.

7. The method according to any of claims 1 to 6, characterized in that the method of applying the mixture to the surface of the polyester composite comprises spraying.

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