Organic tertiary amine / polyether dual-modified organosilicon surfactant as well as preparation method and application thereof

Abstract

The invention discloses an organic tertiary amine / polyether double-modified organic silicon surfactant which is characterized in that the structural formula of the organic tertiary amine / polyether double-modified organic silicon surfactant is # imgabs0 #, the value of m is 0-80, the total value of a and b is 2-40, a is greater than or equal to 1, and b is greater than or equal to 1; x is 6-30, and y is 0-30; r1 is alkyl with the carbon atom number of 1-10 or alkyl alcohol with the carbon atom number of 1-10, and R2 is hydroxyl, methyl, acetyl, amino, butyl, carboxyl or carboxylate radical ions. The modified organic silicon surfactant provided by the invention has the characteristic of variable surface tension under different conditions; the silicone oil has high surface tension at the initial stage of the composite material, so that the fluidity can be improved; along with the increase of the reaction temperature, the tertiary amine group is gradually unblocked, the surface tension of the silicone oil is gradually reduced, and the later emulsifying property of the composite material is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of organic silicon surfactants, and specifically relates to a method for preparing an organic tertiary amine / polyether double-modified organic silicon surfactant, an organic tertiary amine / polyether double-modified organic silicon surfactant prepared by the preparation method, and application of the organic tertiary amine / polyether double-modified organic silicon surfactant in polyurethane materials, especially in hard foams, such as refrigerators, buildings and other insulation materials and soft foam polyurethane sponges such as pillows, sofas and mattresses as a foam stabilizer with self-catalytic properties; coating application, a multifunctional auxiliary agent with leveling and dispersing effects in coatings, and a modified softener with high temperature resistance in textile materials. Background Art

[0002] Rigid polyurethane foam has been used as a high-quality thermal insulation material due to its excellent thermal insulation performance. In the formulation of rigid polyurethane foam, silicone surfactant is used as a foam leveler. Foam levelers play a vital role in the preparation of rigid polyurethane foam. They can promote the uniform distribution of bubbles during the foam generation process, avoid the formation of large bubbles, ensure the fine and uniform foam structure, and thus improve the mechanical strength and thermal insulation performance of the foam material. Foam levelers can also affect the stability and dimensional stability of the foam.

[0003] As the requirements for foam performance continue to increase, the design and synthesis of foam levelers are also constantly improving. Today's foam levelers not only need to have good dispersibility and stability, but also need to have a positive impact on the foam's combustion performance and environmental adaptability while meeting environmental protection requirements.

[0004] For example, some studies have used specific leveling agents to improve the combustion performance of flame-retardant rigid polyurethane foam plastics and reduce smoke generation. In the use of rigid foam silicone oil, there has always been a pair of contradictory parameters: the fluidity of silicone oil and the emulsification of silicone oil. A silicone oil with good fluidity can make the rigid foam combination material flow better in a complex mold, and it is not easy to produce defective products that cannot be filled. Good leveling performance requires that the surface tension of the surfactant should not be too low. On the other hand, if the polyurethane rigid foam wants to have fine pores, the silicone oil needs to have good emulsification properties, and the emulsification performance requires the surfactant surface tension to be as low as possible. Existing silicone surfactants cannot solve this problem.

[0005] Paint is a liquid or solid material applied to the surface of an object. It can solidify into a thin film under certain conditions, thereby achieving protection, decoration or other special functions for the object. The application of paint is extremely wide, covering many fields from daily necessities to industrial equipment, construction and so on. There are many additives used in the paint system, many of which are silicone surfactants, which are used to solve a certain type or some special interface problems in the production, storage, construction, film formation and curing process of the paint. For example, wetting agents solve the problems of interfacial tension and wettability between interfaces; leveling additives solve the problem of interfacial tension gradient difference during the flow or shear film formation of the paint; rheological additives control the viscosity of the paint system through hydrogen bonds and intermolecular forces; defoamers eliminate the foam generated in the paint system and can control the speed of foam generation; dispersants solve the incompatibility between liquid and solid particles, improve their thermodynamic stability, and make the coating surface smooth.

[0006] At present, the functions of these coating additives are often relatively simple. Various additives with different functions need to be added during coating construction, which makes the batching and construction more troublesome. At the same time, the simultaneous use of multiple additives will also have an adverse effect on the mechanical properties of the coating. The reason why additives such as wetting agents, leveling agents, rheological agents and dispersants can play their due role in coatings is that they have unique surface activity.

[0007] For example, the Chinese invention patent for tertiary amine-modified silicone polyether copolymer and its preparation method and application with application number 201911383035.7 discloses a tertiary amine-modified silicone polyether copolymer. In this patent, a silicone polyether copolymer containing an epoxy group at the end of the side chain is obtained by using an allyl polyether having an epoxy group at the end and an allyl polyether having a hydroxyl group or an alkyl group at the end, and then a polyether-modified silicone is prepared by amino-capping. However, the silicone with this structure is still a silicone product modified with a single functional group, and all of its side chains contain allyl polyethers, but it is only amino-capped. In essence, it is still a type of polyether-modified silicone, and the above-mentioned problems cannot be solved.

[0008] The disclosure of the above background technology content is only used to assist in understanding the inventive concept and technical solution of the present invention. It does not necessarily belong to the prior art of this patent application. In the absence of clear evidence that the above content has been disclosed before the filing date of this patent application, the above background technology should not be used to evaluate the novelty and creativity of the present application. Summary of the invention

[0009] In view of this, in order to overcome the defects of the prior art, the present invention provides an organic tertiary amine / polyether dual-modified silicone surfactant, which has polyether and organic tertiary amine groups on different side chains, respectively, and the two functional groups can play different roles in different application scenarios.

[0010] In order to achieve the above object, the present invention adopts the following technical solutions:

[0011] An organic tertiary amine / polyether double-modified silicone surfactant, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0012]

[0013] Wherein, the value of m is 0-80, the sum of a and b is 2-40, and a≥1, b≥1; x is 6-30, y is 0-30; R1 is an alkyl group having 1-10 carbon atoms or an alkyl alcohol having 1-10 carbon atoms, and R2 is a hydroxyl group, a methyl group, an acetyl group, an amino group, a butyl group, a carboxyl group or a carboxylate ion. When R1 is an alkyl alcohol, it preferably has 2-4 carbon atoms.

[0014] An organic tertiary amine / polyether double-modified silicone surfactant, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0015]

[0016] wherein k is 1-10, m is 0-80, the sum of a and b is 2-40, and a≥1, b≥1; x is 6-30, y is 0-30; R1 is an alkyl group having 1-10 carbon atoms or an alkyl alcohol having 1-10 carbon atoms, and R2 is a hydroxyl group, a methyl group, an acetyl group, an amino group, a butyl group, a carboxyl group or a carboxylate ion. Preferably, k is 2-4, and R1 is -CH3 or -CH2CH3.

[0017] The present invention also provides a method for preparing the above-mentioned organic tertiary amine / polyether double-modified silicone surfactant, comprising the following steps:

[0018] Silicone oil, allyl polyether and allyl glycidyl ether are reacted to generate polyether and epoxy-modified silicone, which are then reacted with amine substances to prepare the organic tertiary amine / polyether dual-modified silicone surfactant.

[0019] According to some preferred embodiments of the present invention, the molar ratio of the silicone oil to the total molar ratio of allyl polyether and allyl glycidyl ether is 1:1-1.6.

[0020] According to some preferred embodiments of the present invention, the molar ratio of the allyl polyether to the allyl glycidyl ether is 0.1:0.9-0.9:0.1. That is, the total molar amount of the allyl polyether and the allyl glycidyl ether used to provide double bonds is 1-1.6 times that of the silicone oil, wherein the allyl glycidyl ether accounts for 0.1-0.9 of the total amount of the allyl polyether and the allyl glycidyl ether.

[0021] According to some preferred embodiments of the present invention, the reaction temperature of the silicone oil, allyl polyether and allyl glycidyl ether is 90-110°C and the reaction time is 3-5h. Too high a temperature may cause a risk of side reactions, while too low a temperature may affect the reaction process.

[0022] According to some preferred embodiments of the present invention, the reaction temperature of the polyether and epoxy-modified silicone and the amine substance is 70-90° C. and the reaction time is 5-7 hours.

[0023] According to some preferred implementation aspects of the present invention, the addition ratio of the amine substance is that the molar ratio of the epoxy group in allyl glycidyl ether to the amine substance is 1:1-2. Allyl glycidyl ether and organic tertiary amine are variable groups of hydrophilicity and lipophilicity. If the content of allyl glycidyl ether and organic tertiary amine is too high, the hydrophilicity and water solubility are too poor; if the content is too low, the hydrophilicity cannot be changed by pH value.

[0024] According to some preferred embodiments of the present invention, the silicone oil is a low hydrogen silicone oil, with a molecular weight of 300-5000 and a hydrogen content of 0.01%-0.16%. If the hydrogen content is low, there will be less grafting and the hydrophilicity will be too poor. If the hydrogen content is too high, there will be too many polyether and organic amine groups grafted, and the hydrophilicity will be too strong to play a surface activity and dispersion role.

[0025] According to some preferred embodiments of the present invention, the low hydrogen silicone oil is prepared by the following method: octamethylcyclotetrasiloxane (D4), high hydrogen silicone oil and hexamethyldisiloxane are uniformly mixed, and then prepared under the condition that the catalyst is concentrated sulfuric acid, acidic clay and / or trifluoromethanesulfonic acid.

[0026] According to some preferred embodiments of the present invention, the molecular weight of the allyl polyether is 200-4000. If the molecular weight is too small, it cannot play a dispersing role, and if the molecular weight is too large, it cannot be used due to excessive viscosity.

[0027] According to some preferred embodiments of the present invention, the number of propylene oxide groups contained in the allyl polyether is 0 to 30; and / or the number of ethylene oxide groups contained in the allyl polyether is 6 to 30. The number of propylene oxide and ethylene oxide affects the hydrophilicity and lipophilicity.

[0028] According to some preferred embodiments of the present invention, the end-capping method of the allyl polyether is hydroxyl end-capping, methyl end-capping, acetyl end-capping or butyl end-capping. Different end-capping groups also affect the hydrophilicity.

[0029] According to some preferred embodiments of the present invention, the amine substance is one or more selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminoethylamine, diethylaminopropylamine, diethylaminobutylamine, diethanolamine, dipropanolamine, dibutanolamine, and diisopropanolamine.

[0030] Specifically, when the amine substance is one of dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, and didecylamine, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0031]

[0032] Wherein, R1 is an alkyl group having 1 to 10 carbon atoms;

[0033] When the amine substance is one of diethanolamine, dipropanolamine, dibutanolamine and diisopropanolamine, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0034]

[0035] Wherein, R1 is an alkyl alcohol having 2 to 4 carbon atoms;

[0036] When the amine substance is one of dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminoethylamine, diethylaminopropylamine and diethylaminobutylamine, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0037]

[0038] Wherein, the value of k is 2-4, and R1 is -CH3 or -CH2CH3.

[0039] According to some preferred embodiments of the present invention, a catalyst is added during the process of generating polyether and epoxy-modified silicone, and the catalyst is a chloroplatinic acid isopropanol solution, preferably a 10% chloroplatinic acid isopropanol solution.

[0040] According to some preferred embodiments of the present invention, the catalyst is added in an amount of 1-100 ppm, calculated by weight of platinum.

[0041] In some embodiments of the present invention, the preparation method of the organic tertiary amine / polyether dual-modified silicone surfactant is as follows:

[0042] First, low hydrogen silicone oil, allyl polyether and allyl glycidyl ether are mixed, stirred and heated to 90-110°C, and 1-100ppm (calculated by weight of platinum) of 10% chloroplatinic acid isopropanol solution is added as a catalyst, and the reaction is carried out for 3-5 hours. After the silicon hydrogen content is tested by titration method and qualified, organic amine is added and reacted at 70-90°C for 5-7 hours, and small molecules are removed by vacuum to obtain the reaction product, that is, organic tertiary amine / polyether double modified silicone surfactant.

[0043] The present invention adopts polyether and amine for double modification to obtain cationic nonionic silicone surfactant, and the reaction principle is as follows:

[0044]

[0045] In the formula, k=1-10, preferably 2-4, m=0-80, Z=a+b=2-40, a≥1, b≥1, x=6-30, y=0-30;

[0046] R1 is selected from -(CH2) n CH3, -CH2(CH2) n One or more of OH, n = 0-9;

[0047] R2 is selected from -OH, -CH3, -COCH3, -NH2, -C4H9, -COOH, -COO - One or more of .

[0048] The present invention also provides a modified silicone surfactant prepared by the preparation method as described above and its application in additives, such as a foam stabilizer used in polyurethane foam, a multifunctional additive with leveling and dispersing effects used in coatings, or a softener used in textile materials.

[0049] In some embodiments of the present invention, a (rigid) polyurethane foam and a preparation method thereof are provided. The polyurethane foam comprises the following raw material components in parts by weight:

[0050]

[0051] The foam leveling agent is the above-mentioned modified silicone surfactant.

[0052] The preparation method of polyurethane foam is as follows: weigh polyol, water, catalyst and foam leveling agent, mix them evenly. Quickly add cyclopentane as a blowing agent, stir, then quickly add isocyanate and stir again. Pour the mixture into a preheated mold and quickly seal the mold. After the material is completely cured, remove the plate from the mold. After ripening at room temperature, obtain polyurethane foam.

[0053] In some embodiments, the method for preparing polyurethane foam specifically comprises the following steps:

[0054] Weigh ZS-4110 / ZS-3523 polyol, water, catalyst (PC-5 / 41) and foam leveling agent, and stir to mix evenly. Quickly add cyclopentane, a foaming agent, and stir for 18-25 seconds under high-speed dispersion stirring, then quickly add the corresponding amount of PM-200 and stir at high speed for 3-8 seconds. Pour the mixture into a mold that has been preheated to 48-55°C and quickly seal the mold. After 25-35 minutes, the material is completely cured and the plate is removed from the mold. After aging at room temperature for 20-36 hours, the polyurethane foam is obtained.

[0055] The testing of polyurethane foam includes: preparing samples of polyurethane foam sheets according to the test requirements of thermal conductivity, compression strength and dimensional stability and testing them. The thermal conductivity is tested according to the GB / T 10297 method, the foam density is tested according to the GB / T 6343 method, the foam compression strength is tested according to the GB / T 8813 method, and the dimensional stability is tested according to the GB / T 8811 method.

[0056] In some embodiments of the present invention, a color paste and a preparation method thereof are provided. The color paste comprises the following raw material components in parts by weight:

[0057] Polyether polyol 70-80

[0058] Dispersant 3-6

[0059] Pigment powder 10-25

[0060] The dispersant is the modified silicone surfactant mentioned above.

[0061] The preparation method of the color paste is as follows: first add a dispersant to the polyether polyol, stir evenly and then add the required pigment powder of different colors, add zirconium beads as grinding media after dispersion, grind with an oscillator, filter and discharge to obtain the color paste.

[0062] In some embodiments, the method for preparing the color paste specifically comprises the following steps:

[0063] First add dispersant to polyether polyol, stir evenly and then add pigment powder of different colors. Disperse at 1000-2000rpm for 15-25min, add zirconium beads as grinding medium. Then grind with oscillator for 2-3h, filter and discharge to obtain color paste.

[0064] The testing method for color paste includes: using a cone-plate viscometer to test its viscosity at 25°C, and using a scraper fineness meter to measure the fineness of the color paste. After the color paste is sealed in a 60°C oven for 6 weeks, it is taken out to observe its storage stability and retest the viscosity and fineness of the color paste.

[0065] In some embodiments of the present invention, a color coating and a preparation method thereof are provided. The color coating comprises the following raw material components in parts by weight:

[0066]

[0067] The color paste is the above-mentioned color paste, and the curing agent is TDI.

[0068] The preparation method of the color coating is as follows: polyether polyol is mixed with color paste and T-12, dispersed at a speed of 1000-2000rpm for 3-6min, TDI is added as a curing agent, and after mixing for 25-35s, a fully automatic film scraping machine is used to scrape the coating on the polyester film sheet, the coating thickness can be selected to be 80-150μm, and dried to form a film to obtain a color coating.

[0069] In some embodiments of the present invention, a black color paste and a preparation method thereof are provided. The color coating comprises the following raw material components by weight:

[0070]

[0071] The dispersant is the modified silicone surfactant mentioned above.

[0072] The preparation method of black color paste is as follows: add dispersant to deionized water, stir evenly, add carbon black, disperse at a speed of 1000-2000rpm for 15-25min, add zirconium beads as grinding media, grind with an oscillator for 2-3h, filter and discharge to obtain black color paste.

[0073] The testing method for black color paste includes: using a cone-plate viscometer to test its viscosity at 25°C, and using a scraper fineness meter to measure the fineness of the color paste. After the color paste is sealed in a 60°C oven for 6 weeks, it is taken out to observe its storage stability and retest the viscosity and fineness of the color paste.

[0074] In some embodiments of the present invention, a black coating and a preparation method thereof are provided. The black coating comprises the following raw material components in parts by weight:

[0075] Varnish 70-80

[0076] Black color paste 20-30

[0077] Isocyanate curing agent 8-12

[0078] The black color paste is the above-mentioned black color paste, and the varnish includes the following raw material components by weight:

[0079]

[0080] The preparation method of the black coating is as follows: add water-based acrylic resin, deionized water, thickener, wetting agent and defoamer into a high-speed disperser and disperse at a speed of 1000-2000rpm for 25-35min. Add TDI as a curing agent and black color paste. After 25-35s of mixing, use a fully automatic film scraping machine to scrape the coating on the polyester film. The coating thickness can be selected to be 80-150μm, and dry to form a film to obtain a black coating.

[0081] Principle of the present invention: The organic tertiary amine / polyether dual-modified silicone surfactant of the present invention first reacts silicone oil, allyl polyether and allyl glycidyl ether to generate polyether- and epoxy-modified silicone, so that different side chains of the silicone have polyether groups (allyl polyether) and epoxy groups (allyl glycidyl ether reaction), and then organic amine substances are further connected to the side chains with epoxy groups to form organic tertiary amine groups, thereby obtaining an organic tertiary amine and polyether dual-group modified silicone surfactant. Since two different functional groups, polyether and organic amine, exist on different side chains at the same time, the two functional groups can play different roles in different application scenarios, such as becoming a surfactant with both cationic groups and non-ionic groups in terms of responsiveness to pH; or the two groups can play the roles of solvation chains and fixing groups in coating dispersants, etc.

[0082] Because amines are hydrophilic groups due to the presence of active hydrogen, and tertiary amine groups become lipophilic groups in a non-ionic state because alkyl groups replace hydrogen. After quaternization, tertiary amine groups change from lipophilic groups to hydrophilic groups. In this way, the hydrophilicity and lipophilicity of surfactants can be controlled by the degree of quaternization. At the same time, polyethers are hydrophilic groups; silicones are hydrophobic main chains; allyl glycidyl ether and organic tertiary amines are hydrophilic and lipophilic variable groups. The content of polyether and organic tertiary amine groups needs to be controlled. If the content is too high, the hydrophilicity is too poor and the water solubility is too poor. If the content is too low, the purpose of changing the hydrophilicity by pH value cannot be achieved.

[0083] Due to the implementation of the above technical scheme, the present invention has the following advantages compared with the prior art: the modified silicone surfactant in the present invention has the characteristic of variable surface tension under different conditions; the surface tension of the silicone oil is relatively high at the initial stage of the combined material, which helps to improve fluidity; and as the reaction temperature increases, the tertiary amine group is gradually unblocked, and the surface tension of the silicone oil is gradually reduced, thereby improving the emulsification performance of the combined material in the later stage. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0085] Figure 1 This is a picture of the rigid polyurethane foam sample prepared in Example 5 of the present invention;

[0086] Figure 2 This is a picture of the color paste film sheet prepared in Example 6 of the present invention;

[0087] Figure 3 This is a picture of the film formation of the color paste in the deflocculation and flocculation states of Example 6 of the present invention;

[0088] Figure 4 These are pictures of the black colorant film-forming of Example 7 of the present invention; wherein, the left side is a picture of the acidic carbon black colorant film-forming (unflocculated); the left side is a picture of the alkaline carbon black colorant film-forming (flocculated), and each picture corresponds from left to right to the coating film layers of BYK-190 / Example 2 / Example 4. DETAILED DESCRIPTION

[0089] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0090] The following is the manufacturer information of some reagents used in the examples:

[0091]

[0092] In the process of using silicone oil in rigid foam (polyurethane rigid foam), the fluidity and emulsification of silicone oil are a pair of contradictory parameters. A silicone oil with good fluidity can make the rigid foam combination material flow better in a complex mold, and it is not easy to produce defective products that are not fully filled. Good leveling performance requires that the surface tension of the surfactant cannot be too low; on the other hand, if the polyurethane rigid foam wants to have fine pores, the silicone oil needs to have good emulsification performance, and emulsification performance requires the surfactant surface tension to be as low as possible. Therefore, the core requirements of good fluidity (leveling) and good emulsification performance are contradictory, and it is impossible to have both at the same time.

[0093] Based on such problems, the present invention modifies silicone oil and designs a double-modified silicone surfactant with organic tertiary amine and polyether bifunctional groups to perfectly resolve the contradiction between the two. Since the double-modified silicone surfactant has an organic tertiary amine structure, it has a self-catalytic effect to a certain extent. In the early stage of the composite material, the effect of the silicone oil is consistent with that of the conventional silicone surfactant. At the same time, due to the design of its organic tertiary amine lipophilic structure, the surface tension is higher than that of conventional silicone oil, which helps to improve fluidity. In terms of thermal motion steric hindrance, as the reaction temperature increases, the thermal motion ability of the organic tertiary amine group of the macromolecule on the silicone oil increases, and the role as a catalyst begins to slowly emerge, which can speed up the reaction speed, so that the viscosity of the system begins to rise rapidly, and improves the emulsification performance of the composite material in the later stage.

[0094] Based on the above scheme and the purpose to be achieved, the preparation method of the polyether and organic tertiary amine double-modified silicone surfactant of the present invention specifically comprises the following steps:

[0095] Step 1: Preparation of low hydrogen silicone oil

[0096] The method is prepared by uniformly mixing octamethylcyclotetrasiloxane (D4), high hydrogen silicone oil and hexamethyldisiloxane, and using concentrated sulfuric acid, acidic clay or trifluoromethanesulfonic acid as a catalyst.

[0097] The prepared low-hydrogen silicone oil has a molecular weight of 300-5000 and a hydrogen content of 0.01%-0.16%.

[0098] Step 2: react low hydrogen silicone oil, allyl polyether and allyl glycidyl ether to generate polyether and epoxy modified silicone

[0099] First, hydrogen-containing silicone oil, allyl polyether and allyl glycidyl ether are mixed, stirred and heated to 90-110° C., and 10% chloroplatinic acid isopropanol solution is added as a catalyst, and the mixture is reacted for 3-5 hours.

[0100] The amount of catalyst added is 1-100 ppm, calculated by weight of platinum. The molecular weight of the allyl polyether is 200-4000; the amount of propylene oxide is 0-30, and the amount of ethylene oxide is 6-30 when preparing the allyl polyether; the end-capping method of the allyl polyether is hydroxyl end-capping, methyl end-capping, acetyl end-capping or butyl end-capping.

[0101] Step 3: reacting polyether and epoxy modified silicone with organic amine to prepare organic tertiary amine / polyether double modified silicone surfactant

[0102] Specifically, after the silicon hydrogen is tested to be qualified, an organic amine is added to react at 70-90° C. for 5-7 hours, and small molecules are removed in vacuo to obtain a reaction product, namely a modified organic silicon surfactant.

[0103] The organic amine substance is one or more selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminoethylamine, diethylaminopropylamine, diethylaminobutylamine, diethanolamine, dipropanolamine, dibutanolamine, and diisopropanolamine.

[0104] The structural formula of the prepared organic tertiary amine / polyether double-modified silicone surfactant is as follows:

[0105]

[0106] Among them, the value of k is 1-10, the value of m is 0-80, the total value of a and b is 2-40, and a≥1, b≥1; x is 6-30, y is 0-30; R1 is an alkyl group with 1-10 carbon atoms or an alkyl alcohol with 1-10 carbon atoms, and R2 is hydroxyl, methyl, acetyl, amino, butyl, carboxyl or carboxylate ion.

[0107] When the amine substance is one of dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine and didecylamine, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0108]

[0109] Wherein, R1 is an alkyl group having 1 to 10 carbon atoms;

[0110] When the amine substance is one of diethanolamine, dipropanolamine, dibutanolamine and diisopropanolamine, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0111]

[0112] Wherein, R1 is an alkyl alcohol having 2 to 4 carbon atoms;

[0113] When the amine substance is one of dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminoethylamine, diethylaminopropylamine and diethylaminobutylamine, the structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is:

[0114]

[0115] Wherein, the value of k is 2-4, and R1 is -CH3 or -CH2CH3.

[0116] Example 1

[0117] The preparation method of the organic tertiary amine / polyether double-modified silicone surfactant in this embodiment is as follows:

[0118] First, low hydrogen silicone oil, allyl polyether and allyl glycidyl ether were mixed and stirred and heated to 100°C, and 50ppm (calculated by weight of platinum) of 10% chloroplatinic acid isopropanol solution was added as a catalyst and reacted for 4 hours. After the silicon hydrogen test was qualified, organic amine was added and reacted at 80°C for 6 hours. After the small molecules were removed by vacuum, the reaction product was obtained, namely, organic tertiary amine / polyether double-modified silicone surfactant.

[0119] The molecular weight of the low hydrogen silicone oil is 500, and the hydrogen content is 0.16%; the molecular weight of the allyl polyether is 500, and when preparing the allyl polyether, the amount of propylene oxide a=0, the amount of ethylene oxide b=12, and the end-capping method of the allyl polyether is: hydroxyl end-capping. The organic amine is diethylamine. The feed ratio is shown in Table 1.

[0120] Example 2

[0121] The difference between this embodiment and embodiment 1 is that the molecular weight of the low hydrogen silicone oil in this embodiment is 5000, and the hydrogen content is 0.01%; the molecular weight of the allyl polyether is 200, and when preparing the allyl polyether, the number of propylene oxide a=2, the number of ethylene oxide b=2, and the end-capping method of the allyl polyether is methyl end-capping. The organic amine is dimethylaminoethylamine. The remaining steps and parameters are basically the same as those in embodiment 1, and the feed ratio is shown in Table 1.

[0122] Example 3

[0123] The difference between this embodiment and embodiment 1 is that the molecular weight of the low hydrogen silicone oil in this embodiment is 300, and the hydrogen content is 0.16%; the molecular weight of the allyl polyether is 3000, the amount of propylene oxide a=30, the amount of ethylene oxide b=30 when preparing the allyl polyether, and the end-capping method of the allyl polyether is acetyl end-capping. The organic amine is diethylaminopropylamine. The remaining steps and parameters are basically the same as those in embodiment 1, and the feed ratio is shown in Table 1.

[0124] Example 4

[0125] The difference between this embodiment and embodiment 1 is that the molecular weight of the low hydrogen silicone oil in this embodiment is 1500, and the hydrogen content is 0.03%; the molecular weight of the allyl polyether is 1000, and when preparing the allyl polyether, the amount of propylene oxide a=18, the amount of ethylene oxide b=6, and the end-capping method of the allyl polyether is butyl end-capping. The organic amine is diethanolamine. The remaining steps and parameters are basically the same as those in embodiment 1, and the feed ratio is shown in Table 1.

[0126] Table 1 Feeding parameters in the embodiment

[0127] Unit, g Example 1 Example 2 Example 3 Example 4 Hydrogen silicone oil 74 90 55 130 Allyl glycidyl ether 30 40 55 20 Allyl polyether 80 158 158 258 Organic amine 20 35 45 16

[0128] Example 5 Rigid polyurethane foam application evaluation

[0129] According to the following ingredient table 2, the organic tertiary amine / polyether dual-modified silicone surfactant prepared in the example, the common commercially available foam leveler UR-5960 and other ingredients were mixed to obtain a rigid polyurethane foam composition, and relevant tests were performed.

[0130] Table 2 Ingredients of rigid polyurethane foam composition

[0131]

[0132] The preparation method of the rigid polyurethane foam composition is as follows:

[0133] Weigh 50 g of a total of polyol (ZS-4110, ZS-3523), water, catalyst (PC-5, PC-41), foam leveler UR-5960 or Examples 1-4; mix them uniformly in advance by stirring as component A.

[0134] Rapidly add the blowing agent cyclopentane (CP), stir for 20 seconds under high-speed dispersing stirring, then quickly add the corresponding amount of isocyanate PM-200 and stir at high speed for another 5 seconds.

[0135] Pour the mixture into a mold that has been preheated to 50°C and quickly seal the mold.

[0136] After 30 minutes, the material is completely solidified and the plate is removed from the mold.

[0137] The samples were prepared and tested according to the test requirements of thermal conductivity, compressive strength and dimensional stability. The test results are shown in Table 3 below. Figure 1 shown.

[0138] Among them, the thermal conductivity test method refers to GB / T 10297 polyurethane rigid foam test method, the foam density test should be tested according to GB / T 6343, the foam compression strength test should be tested according to GB / T 8813, and the dimensional stability test should be tested according to GB / T8811.

[0139] Table 3 Rigid polyurethane foam test results

[0140]

[0141] In order to verify the uniform foaming performance and catalyst performance of the organic tertiary amine / polyether dual-modified silicone surfactant, the aged samples were tested for appearance defects, thermal conductivity, tensile strength and dimensional stability.

[0142] from Figure 1It can be seen from the data in Table 3 that the use of organic tertiary amine / polyether dual-modified silicone surfactant can replace the conventional foam leveler UR-5960 (#5); the physical parameters of the prepared polyurethane foam such as density, compressive strength and dimensional stability are also not much different from those of the standard formula UR-5960 (#5).

[0143] At the same time, it was found that the use of organic tertiary amine / polyether dual modified silicone surfactants had an impact on some parameters. The first was the appearance of polyurethane foam. Compared with the 5# control group, the foam without catalyst had a smoother appearance and fewer bubble defects; while the control group using polyurethane catalyst had relatively more defects, and it was found that the defects were mainly concentrated in the front part of the foam, that is, the early stage of foaming, indicating that if the catalytic reaction process is slow at first and then fast, it is easier to reduce the generation of defects. In addition to surface defects, thermal conductivity is also positively correlated with the number of surface defects. The thermal conductivity of samples with fewer defects is also lower than that of samples with more defects.

[0144] The general catalysts are either fast at the beginning and end, which affects the initial fluidity; or slow at the beginning and end, which affects the cross-linking and demolding time at the end. The use of the organic tertiary amine / polyether double-modified silicone surfactant in the embodiment of the present invention can not only replace the traditional polyurethane catalyst, but also improve the foaming defects in the mold due to its slow early stage and fast later stage, which can quickly cross-link and demold and improve efficiency. The prepared foam has a better appearance, fewer surface defects, and better thermal conductivity.

[0145] Example 6 Coating Application Evaluation (Color Paste)

[0146] (I) Various organic pigments were selected as the color paste for preparing polyether system coatings. The color paste preparation formula is shown in Table 4 below.

[0147] The preparation method of the color paste is as follows:

[0148] First add dispersant (BYK-9076, organic tertiary amine / polyether double modified silicone surfactant prepared in Example 1 or Example 3) to the polyether polyol, stir evenly and add pigment powder of different colors as required. Disperse at a speed of 1000-2000rpm for 15-25min, and add zirconium beads as grinding media. Then grind with an oscillator for 2.5h, filter and discharge, test its viscosity at 25°C using a cone plate viscometer, and measure the fineness of the color paste using a scraper fineness meter. After the above color paste is sealed in a 60°C oven for 6 weeks, take it out to observe its storage stability and retest the viscosity and fineness of the color paste. The results are shown in Table 6.

[0149] Table 4: Formula of coating color paste

[0150]

[0151] (ii) The polyether polyol, the above color paste and T-12 were mixed according to the formula in Table 5, dispersed at a speed of 1000-2000rpm for 5min, TDI was added as a curing agent, mixed for 30s, and a 100μm coating was applied on the polyester film using a fully automatic film scraper. The film was dried at room temperature for 24h to form a colored coating. The condition, transparency and hue of the paint film were observed with the naked eye, and its glossiness was measured. The results are as follows: Figure 2 , Figure 3 And as shown in Table 6.

[0152] Table 5 Polyether color paste film-forming formula

[0153]

[0154] Table 6 Test results of color paste and polyether color paste film formation (color coating)

[0155]

[0156]

[0157] From the data in Table 6, it can be seen that although the permanent orange, pigment red and permanent violet ground in Example 1 all underwent flocculation, particulate matter also appeared in the prepared coating film. Figure 3 The red color paste coating and the flocculated color paste coating after storage are shown in Figure 2. However, it can be found that the permanent purple paste ground by BYK-9076 also flocculated, but the color paste ground by Example 3 did not flocculate. Figure 2 As shown, it is shown that Example 3 has good dispersibility and storage stability for all five color pastes, which has surpassed the level of the professional dispersant BYK-9076.

[0158] Example 7 Coating Application Evaluation (Black Color Paste)

[0159] (i) Select carbon black with different pH values ​​and prepare water-based black color paste according to the formula in Table 7.

[0160] The preparation method is as follows: add a dispersant (BYK-190, an organic tertiary amine / polyether double-modified silicone surfactant prepared in Example 2 or Example 4) to deionized water, stir evenly, and then add the required carbon black. Disperse at a speed of 1000-2000rpm for 15-25min, and add zirconium beads as grinding media. Then grind with an oscillator for 2.5h, and discharge after filtration. Use a cone and plate viscometer to test its viscosity at 25°C, and use a scraper fineness meter to measure the fineness of the color paste. After the above color paste is sealed and placed in a 60°C oven for 6 weeks, take it out to observe its storage stability and retest the viscosity and fineness of the color paste. The results are shown in Table 9.

[0161] Table 7 Black water-based color paste formula

[0162]

[0163]

[0164] (ii) Add black color paste, water-based acrylic resin (Allnex 6511), deionized water, thickener (XS71), wetting agent (UL-353) and defoamer (DS-5624) into a high-speed disperser according to the formula in Table 8, and disperse at a speed of 1000-2000rpm for 30 minutes. Add TDI as a curing agent and black color paste. After mixing evenly for 30 seconds, use a fully automatic film scraper to scrape a 100μm coating on the polyester film. Dry at room temperature for 24 hours to obtain a black coating. Observe the condition and transparency of the paint film with the naked eye, measure its gloss using a gloss meter, and measure its Lab value using a colorimeter. The results are as follows: Figure 4 , as shown in Table 9.

[0165] Table 8 Carbon black water-based color paste film-forming (black coating) formula

[0166]

[0167] The 75 parts of varnish formula in the water-based black color paste formula in the last column of the table are selected from one of BYK-9076 varnish formula 01, Example 2 varnish formula 02, and Example 4 varnish formula 03 in the first three columns of the table.

[0168] Table 9 Test results of carbon black slurry and film formation

[0169]

[0170]

[0171] Table 9 shows the test results of water-based black color paste and coating performance after 6 weeks of storage. The results show that Example 2 and Example 4 are better than the conventional dispersant (BYK-190) in the acidic color paste (FW-200, pH = 2.5), and other systems (N-19, pH = 10.5, JY-6606, pH = 7.5) are slightly worse than the conventional dispersant (BYK-190). Specifically: the alkaline and neutral black color pastes of Example 2 and Example 4 all flocculate and coarse ( Figure 4), although the color paste using BYK-190 did not flocculate, the particle size began to coarsen from the fineness. On the contrary, the acidic black color paste was not coarsened. The black color paste using Examples 2 and 4 did not coarsen basically, the L value did not change much, and the b value was also negative and blue. This is due to the special structure of Examples 2 and 4. Under acidic conditions, the organic amine exhibits a cationic structure. In addition to the presence of steric hindrance, the repulsion of positive charges is increased, which increases the stability of the acidic color paste. On the other hand, although the application effect of the organic tertiary amine / polyether double-modified silicone surfactant in the example is slightly worse than that of BYK-190 in alkaline and neutral systems, the dispersant BYK-190 cannot be applied to organic pigment systems, while the organic tertiary amine / polyether double-modified silicone surfactant in the present application can be applied to colored organic pigments (Example 6), which is impossible for BYK-190.

[0172] That is, the organic tertiary amine / polyether dual-modified silicone surfactant in this application can be applied to a variety of dispersion systems. In the process of dispersing organic pigments, due to the existence of the dual modification results, the two groups play different roles. The tertiary amine exists as a hydrophobic group and can adsorb to the organic pigment, while the polyether can act as a solvation chain to ensure dispersion in water. The combination of the two can effectively disperse low-polarity color pigments in water; and for the dispersion of carbon black, especially in an acidic environment, after the tertiary amine becomes a quaternary ammonium salt, the cationic group can better combine with the carboxylic acid on the acidic carbon black to become a pigment adsorption group, and the polyether still acts as a solvation chain to achieve a stable water dispersion effect.

[0173] The double-modified silicone surfactant in this patent contains two different functional groups, polyether and organic amine. The two functional groups can play different roles in different application scenarios. For example, the responsiveness to pH makes it a surfactant with both cationic groups and non-ionic groups. In coating dispersants, the two groups can play the roles of solvation chains and fixing groups respectively.

[0174] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

[0175] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. An organic tertiary amine / polyether double-modified silicone surfactant, characterized in that: The structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is: Among them, the value of m is 0-80, the total value of a and b is 2-40, and a≥1, b≥1; x is 6-30, y is 0-30; R1 is an alkyl group with 1-10 carbon atoms or an alkyl alcohol with 1-10 carbon atoms, and R2 is hydroxyl, methyl, acetyl, amino, butyl, carboxyl or carboxylate ion.

2. An organic tertiary amine / polyether double-modified silicone surfactant, characterized in that: The structural formula of the organic tertiary amine / polyether double-modified silicone surfactant is: Among them, the value of k is 1-10, the value of m is 0-80, the total value of a and b is 2-40, and a≥1, b≥1; x is 6-30, y is 0-30; R1 is an alkyl group with 1-10 carbon atoms or an alkyl alcohol with 1-10 carbon atoms, and R2 is hydroxyl, methyl, acetyl, amino, butyl, carboxyl or carboxylate ion.

3. A method for preparing the organic tertiary amine / polyether double-modified silicone surfactant according to claim 1 or 2, characterized in that: The steps include: Silicone oil, allyl polyether and allyl glycidyl ether are reacted to generate polyether and epoxy-modified silicone, which are then reacted with amine substances to prepare the organic tertiary amine / polyether dual-modified silicone surfactant.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the silicone oil to the total mole of allyl polyether and allyl glycidyl ether is 1:1-1.

6.

5. The preparation method according to claim 3, characterized in that: The molar ratio between the allyl polyether and the allyl glycidyl ether is 0.1:0.9-0.9:0.

1.

6. The preparation method according to claim 3, characterized in that: The reaction temperature of the silicone oil, allyl polyether and allyl glycidyl ether is 90-110° C. and the reaction time is 3-5 hours.

7. The preparation method according to claim 3, characterized in that: The addition ratio of the amine substance is such that the molar ratio of the epoxy group in allyl glycidyl ether to the amine substance is 1:1-2.

8. The preparation method according to claim 3, characterized in that: The reaction temperature of the polyether and epoxy-modified silicone and amine substances is 70-90° C. and the reaction time is 5-7 hours.

9. The preparation method according to claim 3, characterized in that: The silicone oil is low-hydrogen silicone oil with a molecular weight of 300-5000 and a hydrogen content of 0.01%-0.16%.

10. The preparation method according to claim 9, characterized in that: The low hydrogen silicone oil is prepared by the following method: octamethylcyclotetrasiloxane, high hydrogen silicone oil and hexamethyldisiloxane are uniformly mixed, and then the mixture is prepared under the condition that the catalyst is concentrated sulfuric acid, acidic clay and / or trifluoromethanesulfonic acid.

11. The preparation method according to claim 3, characterized in that: The molecular weight of the allyl polyether is 200-4000.

12. The preparation method according to claim 3, characterized in that: The number of propylene oxide groups contained in the allyl polyether is 0-30.

13. The preparation method according to claim 3, characterized in that: The number of ethylene oxide groups contained in the allyl polyether is 6-30.

14. The preparation method according to claim 3, characterized in that: The end-capping method of the allyl polyether is hydroxyl end-capping, methyl end-capping, acetyl end-capping, amine end-capping, carboxyl end-capping, carboxylate end-capping or butyl end-capping.

15. The preparation method according to claim 3, characterized in that: The amine substance is one or more selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminoethylamine, diethylaminopropylamine, diethylaminobutylamine, diethanolamine, dipropanolamine, dibutanolamine, and diisopropanolamine.

16. The preparation method according to claim 3, characterized in that: A catalyst is added during the process of generating polyether and epoxy-modified silicone, and the catalyst is an isopropanol solution of chloroplatinic acid.

17. The preparation method according to claim 16, characterized in that: The catalyst is added in an amount of 1-100 ppm, calculated by weight of platinum.

18. Use of the organic tertiary amine / polyether dual-modified silicone surfactant as claimed in claim 1 or 2 or the organic tertiary amine / polyether dual-modified silicone surfactant prepared by the preparation method according to any one of claims 3 to 17 in an auxiliary agent.

19. The use of the organic tertiary amine / polyether dual-modified silicone surfactant in an auxiliary agent according to claim 18, characterized in that: The auxiliary agent is a foam stabilizer used in polyurethane foam, a multifunctional auxiliary agent with leveling and dispersing effects used in coatings, or a softener used in textile materials.

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