Solvent-free branched siloxane multipolymer and preparation method thereof

Abstract

The invention provides a solvent-free branched siloxane multipolymer and a preparation method thereof. Polysiloxane with a specified structure and a hydrogen-containing group is obtained through directional polymerization, and then the polysiloxane reacts with long-chain olefin with large molecular weight and other monomer compounds with unsaturated bond structures to obtain a prepolymer; and carrying out block polymerization with a compound with a 'T-structure' group to obtain the product in the patent in a solvent-free state. The polymer obtained by the reaction is matched with different types of plastic resin, and the functional master batch can be prepared by processing, so that the internal and external lubrication can be enhanced, the internal stress is reduced, the equipment wear is reduced, the service life is prolonged, the production efficiency is improved, the wettability of various filling powder can be increased, the powder filling amount is obviously increased, and the cost is effectively reduced; and meanwhile, the excellent effects of reducing the influence of powder filling on the mechanical property of the plastic and the like can be achieved.

Description

Technical Field

[0001] The present invention relates to the field of new materials, and particularly relates to a solvent-free branched siloxane copolymer and a preparation method thereof. Background Art

[0002] After long-term development, the plastic industry has formed a relatively complete industrial system and has become a basic material industry on a par with steel, cement, and wood. As a new material, its application fields have far exceeded those of the above three materials. Since the beginning of the 21st century, the Chinese plastic industry has achieved remarkable achievements and realized a historic leap. As one of the pillar industries in the light industry, the plastic industry has maintained a growth rate of over 10% in recent years. While maintaining a relatively fast development speed, its economic efficiency has also been newly improved. The total output value of enterprises above designated size in the plastic products industry ranks third among the 19 major light industries, with a product sales rate of 97.8%, higher than the average level of the light industry. From the perspectives of synthetic resin, plastic machinery, and plastic product production, it shows a strong development momentum of the Chinese plastic industry.

[0003] Plastic lubricants are one of the indispensable additives in modern plastic processing technologies. Polymers usually have a relatively high viscosity after melting, and additives are required to be added during the processing to improve lubricity, reduce friction, and lower interfacial adhesion performance. Such additives are lubricants. They can improve the processing speed, reduce energy consumption, and improve the quality of plastic products, especially the appearance quality.

[0004] There are many types of lubricants, and the two most commonly used classification methods are as follows. One is classification according to the components of lubricants, mainly including hydrocarbons, aliphatic amides, aliphatic acids, esters, alcohols, metal soaps, and composite lubricants, etc. The other is classification according to the functions of lubricants, which can be divided into internal lubricants and external lubricants.

[0005] Internal lubricants are usually small molecular organic compounds with polar groups. According to the principle of similar compatibility, internal lubricants have good compatibility with polar resins and can penetrate between and into the particles of each layer of the resin, reducing the intermolecular forces between molecular chain segments, thereby reducing the "plasticization torque". Before resin plasticization, a complex bond is formed after chemical adsorption between the resin and the internal lubricant, weakening the friction between resin chain segments; after resin plasticization, the polar groups of the internal lubricant weaken the intermolecular and intermolecular chain segment forces in the melt, making the resin melt flow easily, reducing the melt viscosity, and playing the role of internal lubrication.

[0006] External lubricants are generally non-polar or low-polarity compounds with low surface tension. They have poor compatibility with strongly polar resins and are easily excluded by strongly polar resins to the interface of the system, forming a thin external lubricating film, which can reduce the friction between the resin and the surface of metal processing equipment and delay the resin plastification. Before the resin plastifies, the external lubricant wraps on the surface of resin particles to reduce the friction between resin particles; after the resin plastifies, the thin film formed on the surface of the resin melt can reduce the adhesion and friction of the resin to the metal surface.

[0007] The internal and external lubrication functions of lubricants are determined by their chemical composition, polarity, and solubility in the polymer melt. If only the single lubrication effect of the lubricant is required, their selection is very simple. However, in most cases, it is best to adjust their internal and external lubrication effects to a certain degree. The conditions that an ideal plastic lubricant should have are as follows: excellent and long-lasting lubrication function; good compatibility with the polymer, balanced internal and external lubrication effects, no impact on the transparency of the resin, no blooming, not easy to scale, good compatibility with other additives; small surface attraction, good extensibility at the interface, easy to form an interface layer; excellent thermal stability function, no decomposition, evaporation, or reduction of various excellent functions of the polymer during the processing and molding process, and no impact on the reprocessing function of the product; non-toxic, pollution-free, and non-corrosive to equipment.

[0008] Traditional plastic lubricants, such as paraffin hydrocarbons, fatty acids and their esters, metal soaps, low-molecular-weight resins, etc., have certain limitations and disadvantages in terms of lubrication persistence, stability, safety, and compatibility with other additives due to their simple product structures and relatively single properties, and can no longer meet the higher requirements of plastic processing. For example, paraffin hydrocarbon lubricants are relatively widely sourced and inexpensive, but their properties are relatively single. They usually need to be used in combination with other additives. As the carbon number increases, their compatibility with the plastic system deteriorates, and at the same time, it affects the transparency of the product. When the dosage is large, it is easy to cause stickiness and press marks; the most commonly used fatty acid is stearic acid. When the dosage is small, it has an anti-press mark effect, but when the dosage is large, it is easy to cause blooming and affect the transparency of the product.

[0009] Organic silicon materials are a new type of material with relatively fast application development and are widely used in the fields of petroleum, chemical industry, textile, construction, food, medicine, etc. In recent years, the excellent properties of organic silicon materials have also attracted the attention of the domestic and foreign plastic processing industries and have become a hot spot in current plastic material research.

[0010] Common silicone-based lubricants on the market at present are mainly silicone masterbatches, which are composed of siloxanes, resin carriers, and other additives. As a lubricant, it can reduce the friction coefficient, improve lubricity, enhance the processing fluidity of products, reduce losses, and minimize equipment friction. It is widely used in the processing of thermoplastics such as PP, PE, EVA, PA, and PC, and can basically meet the current application requirements in the plastic field. However, silicone masterbatches also have obvious defects and deficiencies during application. Firstly, there is the issue of the selection of the functional main material, siloxane. The intermolecular forces between siloxane molecules are relatively strong, and the compatibility between the silicon-oxygen bond and the carbon-carbon bond of the resin material is poor. Therefore, it is not easy to disperse evenly by physical methods. If low-chain liquid siloxanes are selected, the low-surface-energy liquid siloxanes migrate to the surface layer of plastic products during use, resulting in oil bleeding and affecting the adhesion and surface secondary processing of plastic products. If high-chain siloxanes are selected, the dispersibility is poor, and it is difficult to play an effective lubricating role. Secondly, there is the compatibility of the resin carrier. Currently, the commonly used resin carriers are PP and PE, which have good compatibility with conventional plastics such as PP, PE, PA, PC, and EVA, but have poor compatibility with special plastic resins such as PBT, PTFE, and POM, easily leading to surface delamination and easy peeling of the products.

[0011] Therefore, there is an urgent need in the market for a type of high-performance silicone-based lubricant that can not only meet the basic requirements of isolation and lubrication, but also have good compatibility with resins, balanced internal and external lubrication effects, and good compatibility with other additives. The solvent-free branched siloxane copolymer of this patent is such an additive, which can relatively evenly meet the requirements in various aspects. Summary of the Invention

[0012] The present invention provides a solvent-free branched siloxane copolymer and its preparation method. A polysiloxane with a hydrogen-containing group of a specified structure is obtained through stereospecific polymerization, and then it reacts with a long-chain olefin with a large molecular weight and other monomer compounds with unsaturated bond structures to obtain a prepolymer, and then undergoes block polymerization with a compound with a T-structured group to obtain the product of this patent in a solvent-free state.

[0013] The present invention provides a solvent-free branched siloxane copolymer, which has the following molecular structural formula:

[0014] MAaBbCcDdEeFfM

[0015] Wherein:

[0016] In the formula, M represents an organosilicon group, and its structural form is

[0017] In the formula, A represents a short-chain alkyl organosilicon group, and its structural form is

[0018] wherein R1 is a short-chain alkyl group, —C n H 2n+1, , where n = 8, 12, 14;

[0019] In the formula, B represents a long-chain alkyl group-containing silicone group, and the structural form is

[0020] wherein R2 is a long-chain alkyl group, —C m H 2m+1, , where m = 20 - 24;

[0021] C in the formula represents an ester hydrocarbon group-containing silicone group, wherein R3 is an alkyl group, —C k H 2k+1 , where k = 4, 8, 12;

[0022] D in the formula represents an aryl group-containing silicone group, and the structural form is

[0023] E in the formula represents a vinyl group-containing unsaturated bond-containing silicone structural group, and the structural form is;

[0024]

[0025] F in the formula represents an aryl group-containing silicone group, and the structural form is

[0026] In the formula, a, b, c, d, e, and f are the relative amounts of each unit group in the invention molecule, and the calculated value is retained to one decimal place, where: a = 1 - 15; b = 5 - 20; c = 1 - 5; d = 1 - 10; e = 1 - 10; f = 20 - 85.

[0027] Optionally, the A group in the invention is obtained by hydrosilylation reaction from the following raw materials: C n H 2n , where n = 8, 12, 14.

[0028] Optionally, the B group in the invention is obtained by hydrosilylation reaction from the following raw materials: C n H 2n , where n = 20 - 24.

[0029] Optionally, the C group in the invention is obtained by hydrosilylation reaction from a methacrylate ester having the following structure:

[0030] Butyl methacrylate, isooctyl methacrylate, lauryl methacrylate.

[0031] Optionally, the D group in the invention is obtained by polymerization reaction from an organosilicon monomer having the following structure and an intermediate process product:

[0032] Or

[0033] Optionally, the E group in the invention is obtained by polymerizing an organosilicon monomer having the following structure with an intermediate product:

[0034] Or

[0035] Optionally, the F structural unit is block copolymerized on the main chain of the entire long-chain alkane siloxane copolymer molecule, and the molar unit ratio of the F structural unit in the entire long-chain alkane siloxane copolymer molecule is 20-85%.

[0036] Optionally, the B structural unit is a side-chain modified structural unit of the entire long-chain alkane siloxane copolymer molecule, and the molar unit ratio of the B structural unit in the entire long-chain alkane siloxane copolymer molecule is 5-20%.

[0037] Optionally, the D structural unit is block copolymerized on the main chain of the entire long-chain alkane siloxane copolymer molecule, and the molar unit ratio of the D structural unit in the entire long-chain alkane siloxane copolymer molecule is 1-10%.

[0038] Optionally, the E structural unit is block copolymerized on the main chain of the entire long-chain alkane siloxane copolymer molecule, and the molar unit ratio of the E structural unit in the entire long-chain alkane siloxane copolymer molecule is 1-10%.

[0039] The present invention also provides a preparation method of the above long-chain alkane siloxane copolymer. The preparation method (example) includes the following steps:

[0040] (1) Preparation of hydrogen-containing siloxane polymer:

[0041] Add 45 g of a side-chain highly hydrogenated polysiloxane with Si-H structure, 153 g of octamethylcyclotetrasiloxane, and 2 g of hexamethyldisiloxane into a glass or stainless steel reaction kettle with a strong stirring device. Stir and heat up to 80-90 °C, then add a catalyst accounting for 0.3% of the total mass in the kettle, keep the temperature unchanged, and continuously react for 5 h. After the reaction, remove the catalyst, pump the material into a low-boiling removal kettle, continuously stir during this process, heat to 120 °C, turn on the cooling circulating water, nitrogen, and vacuum pump, and perform vacuum distillation to remove the unreacted low-boiling substances. This process lasts for 2 h to obtain a hydrogen-containing siloxane polymer M1;

[0042] (2) Preparation of long-chain alkyl ester group structure siloxane copolymer:

[0043] The long-chain olefin monomer, short-chain olefin monomer, and acrylate monomer are respectively subjected to dehydration pretreatment. The specific operation is as follows: Add the material into a glass or stainless-steel reaction kettle equipped with a strong electric stirring device, stir and heat to 100 - 110 °C, and carry out vacuum dehydration for 1 - 1.5 h under the condition of -0.1 MPa. Then cool down to 40 - 50 °C for standby;

[0044] Add 150 g of a hydrogen-containing siloxane polymer M1 with an Si-H structure into a glass or stainless-steel reaction kettle equipped with a strong stirring device. Put in various monomers that have been dehydrated. The total molar amount of various monomers is 0.6 mol. Stir and heat up to 90 - 100 °C, and pass N 2, , and then add an ethanol dispersion of an organoplatinum catalyst accounting for 0.03% of the total mass in the kettle. During the reaction process, the temperature of the system automatically rises, up to 130 - 150 °C at most. During this process, keep stirring and carry out heat preservation reaction for 2 - 3 h. After the reaction ends, turn on the cooling circulating water, nitrogen, and vacuum pump, and carry out vacuum distillation at a constant temperature of 160 °C to remove unreacted low-boiling substances. This process is continuously carried out under N2 protection, and continuous vacuum distillation is carried out for 2 h to obtain a long-chain alkane siloxane copolymer M2.

[0045] (3) Preparation of a multi-modified siloxane copolymer:

[0046] Add 100 g of the long-chain alkyl ester group structure siloxane copolymer M2 obtained in the above (2), 8 g of a structure of CH2=CHSi(OEt)3, and 3 g of a structure of PhSi(OEt)3. Keep stirring, add an appropriate amount of catalyst, and slowly heat up to 80 - 100 °C while stirring. React at a constant temperature for 3 h. The viscosity of the system begins to change, and the overall system begins to be transparent and homogeneous. After the system is stable, add a neutralizing reagent to the reaction vessel to remove the catalyst and keep stirring for 1 h. After the reaction ends, heat up to 180 °C and connect the condensation device, turn on the vacuum, and carry out vacuum distillation for 3 h to distill out the low-boiling substances in the system, and then a branched siloxane multi-copolymer M3 can be obtained.

[0047] The catalysts used in the preparation of the hydrogen-containing siloxane polymer are: trifluoromethanesulfonic acid, sulfuric acid, cation exchange resin, acidified activated clay.

[0048] Organic palladium and organic platinum include any one of the following: palladium oxide (PdO), palladium hydroxide (Pd(OH)2), palladium chloride (PbCl2), sodium tetranitropalladate (Na2Pd(NO3)4), chloroplatinic acid (H2PtCl6).

[0049] The catalysts used in the preparation of the branched siloxane multi-copolymer are: KOH, NaOH, NH4OH(CH3)4, etc.

[0050] The above special molecular structure endows it with the dual functions of organic and inorganic substances. It not only has the low surface tension, low surface energy, temperature and weather resistance, and physiological and biological characteristics based on silicon materials, but also, through modification, is endowed with excellent application characteristics required by the plastics industry. With the molecular flexibility and thermal stability of the siloxane segments in the invention, it can be quickly dispersed in the molten plastic fluid, better improving the flow lubricity of the molten resin, reducing processing energy consumption, and prolonging the service life of processing machinery. By adjusting the main chain structure of the siloxane in the invention and the types and ratios of the organic group side chains, the compatibility of the invention with different types of resins can be improved. By adjusting the structural types of the mutual block copolymerization of the siloxane and the organic structure in the invention, the internal and external lubrication effects can be balanced, so as to achieve the purposes of promoting melting, improving color and luster, increasing gloss, avoiding degradation, increasing the toughness of products, reducing processing energy consumption, and improving processing rate.

[0051] The polymer obtained from the above reaction is combined with different types of resins and can be processed into functional masterbatches through processing. It can not only reduce internal stress, improve production efficiency, but also increase the wettability of various filling powders, significantly increase the powder filling amount, effectively reduce costs, and at the same time can also reduce the impact of powder filling on the mechanical properties of plastics. The processed and formed material has a smooth and moist surface, a good feel, and endows the material with certain waterproof, anti-fouling and scratch-resistant properties. This material has outstanding advantages in the application of the rubber and plastics industry. Detailed implementation mode

[0052] The following are specific embodiments of the present invention in combination with the above-mentioned invention content. It should be noted that the embodiments are only individual examples of the invention, which are used to further elaborate the present invention rather than limit the scope of the present invention.

[0053] Example 1:

[0054] (1) Preparation of hydrogen-containing siloxane polymer:

[0055] Add 100 g of side-chain highly hydrogenated polysiloxane (Dow Chemical Company, USA), 200 g of octamethylcyclotetrasiloxane (Dow Chemical Company, USA), and 1 g of hexamethyldisiloxane (Chengdu Guibao Technology Co., Ltd.) into a glass or stainless-steel reaction kettle with a strong stirring device, stir and heat up to 80-90 °C, then add 10 g of acidic activated clay, keep the temperature unchanged, and continuously react for 3-8 h. After the reaction, remove the catalyst, pump the material into the de-low kettle, continuously stir during this process, heat to 110-130 °C, turn on the cooling circulating water, nitrogen, and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process lasts for 2 h to obtain the hydrogen-containing siloxane polymer M11 for use. This polymer is not taken out (only take a small amount for the content determination of -SiH groups when necessary);

[0056] (2) Preparation of long-chain alkane siloxane copolymer:

[0057] The long-chain olefin monomer, short-chain olefin monomer and acrylate monomer are respectively subjected to dehydration pretreatment. The specific operation is as follows: Add the material into a glass or stainless steel reaction kettle equipped with a powerful electric stirring device, stir and heat to 100-110°C, and carry out vacuum dehydration for 1-1.5 h under the condition of -0.1 MPa. Then cool down to 40-50°C for standby.

[0058] In the prepolymer M11 reaction kettle, put in various monomers that have been dehydrated. The amounts of each monomer are as follows: 400 g of long-chain olefin C 20 H 40 -C 24 H 48 (Shanghai Qicheng), 40 g of short-chain olefin C 14 H 28 (Shanghai Qicheng), 25 g of butyl methacrylate (Shandong Guohua Chemical). Stir and heat up to 80°C, introduce N 2, , and then add 0.5 g of an isopropanol dispersion of platinum catalyst (the dispersion concentration is 1%). During the reaction process, the temperature of the system automatically rises to a maximum of 150°C. During this process, keep stirring and carry out the insulation reaction for 2-3 h. After the reaction is completed, turn on the cooling circulating water, nitrogen and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process is continuously carried out under N2 protection, and continuous vacuum distillation is carried out for 5 h to obtain the long-chain alkane siloxane copolymer M12.

[0059] In the prepolymer M12 reaction kettle, put in various monomers. The amounts of each monomer are as follows: 15 g of vinyltriethoxysilane (Shandong Guike), 20 g of phenyltriethoxysilane (Shandong Guike), 10 g of hydroxyl-terminated silicone oil (Dow Chemical Company, USA). Stir and heat up to 80°C, introduce N2, and then add tetramethylammonium hydroxide. During the reaction process, the system gradually becomes homogeneous, and the constant-temperature reaction is carried out for 3 h. After the reaction is completed, turn on the heating, keep the temperature at 160°C for 2 h. After the end, turn on the cooling circulating water, nitrogen and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process is continuously carried out under N2 protection, and continuous vacuum distillation is carried out for 5 h to obtain the target product M13 of the present invention.

[0060] The value ranges of each material in Example 1 are listed as follows:

[0061]

[0062]

[0063] The above formula shows that the chemical structural formula of the product of this invention is schematically as follows:

[0064] MAaBbCcDdEeFfM

[0065] Each group in the above formula represents the following respectively:

[0066] A is n-tetradecyl siloxy The number of group units is 2.5, that is, a1 = 2.5, within the range of the inventive unit 1 - 15, and the mass ratio is 4.93%, within the range of the design ratio 3 - 10%.

[0067] B is n-eicosyl to n-tetracosyl siloxy Wherein R2 = 20 - 24, the number of group units is 16.5, that is, b1 = 16.5, within the range of the inventive unit 5 - 20, and the mass ratio is 49.32%, within the range of the design ratio 25 - 55%;

[0068] C is the hydrosilylation structure of butyl methacrylate The number of group units is 2.2, that is, c1 = 2.2, within the range of the inventive unit 1 - 5, and the mass ratio is 3.08%, within the range of the design ratio 1 - 5%;

[0069] D is phenyl siloxy The number of group units is 1.5, that is, d1 = 1.5, within the range of the inventive unit 1 - 10, and the mass ratio is 2.47%, within the range of the design ratio 1 - 10%;

[0070] E represents a vinyl organosilicon group, and its structural form is The number of group units is 1, that is, e1 = 1, within the range of the inventive unit 1 - 10, and the mass ratio is 1.85%, within the range of the design ratio 1 - 10%.

[0071] F represents an organosilicon group, and its structural form is The number of group units is 40, that is, f1 = 40, within the range of the inventive unit 20 - 85, and the mass ratio is 25.9%.

[0072] Example 2:

[0073] (1) Preparation of hydrogen-containing siloxane polymer:

[0074] Add 100 g of side-chain hydrogen-rich polysiloxane (Dow Chemical Company, USA), 500 g of octamethylcyclotetrasiloxane (Dow Chemical Company, USA), and 10 g of hexamethyldisiloxane (Chengdu Guibao Science & Technology Co., Ltd.) into a glass or stainless-steel reaction kettle equipped with a strong stirring device. Stir and heat up to 80 - 90 °C, then add 10 g of acidic activated clay, keep the temperature unchanged, and continuously react for 3 - 8 h. After the reaction ends, remove the catalyst, pump the material into the low-boiling removal kettle, continuously stir during this process, heat to 110 - 130 °C, turn on the cooling circulating water, nitrogen, and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process lasts for 2 h to obtain the hydrogen-containing siloxane polymer M21 for use. This polymer is not taken out (only take a small amount for the determination of the content of -SiH groups when necessary);

[0075] (2) Preparation of long-chain alkane siloxane copolymer:

[0076] Conduct dehydration pretreatment on long-chain olefin monomers, short-chain olefin monomers, and acrylate monomers respectively. The specific operation is as follows: Add the materials into a glass or stainless-steel reaction kettle equipped with a strong electric stirring device, stir and heat to 100 - 110 °C, and carry out vacuum dehydration for 1 - 1.5 h under the condition of -0.1 MPa, then cool down to 40 - 50 °C for use;

[0077] In the pre-polymer M21 reaction kettle, put in various monomers that have been dehydrated. The amounts of each monomer are 200 g of long-chain olefin C 20 H 40 -C 24 H 48 (Shanghai Qicheng), 75 g of short-chain olefin C8H 16 (Shanghai Qicheng), 60 g of isooctyl acrylate (Shandong Guohua Chemical), stir and heat up to 80 °C, introduce N 2, , then add 0.3 g of an isopropanol dispersion of platinum catalyst (the dispersion concentration is 1%). During the reaction process, the temperature of the system automatically rises to a maximum of 150 °C. Continuously stir during this process and keep the temperature for reaction for 2 - 3 h. After the reaction ends, turn on the cooling circulating water, nitrogen, and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process is continuously carried out under N2 protection and the vacuum distillation lasts for 5 h to obtain the long-chain alkane siloxane copolymer M22.

[0078] In the prepolymer M22 reactor, various monomers are put in. The amounts of each monomer are as follows: 35 g of vinyltrimethoxysilane (Shandong Silicate), 10 g of phenyltrimethoxysilane (Shandong Silicate), and 10 g of hydroxyl-terminated silicone oil (Dow Chemical Company, USA). Stir and heat up to 80 °C, introduce N2, and then add tetramethylammonium hydroxide. During the reaction process, the system gradually becomes homogeneous. React at a constant temperature for 3 h. After the reaction ends, start heating up, keep the temperature at 160 °C for 2 h. After that, turn on the cooling circulating water, nitrogen, and vacuum pump for vacuum distillation to remove unreacted low-boiling substances. This process is continuously carried out under N2 protection, and continuous vacuum distillation is carried out for 5 h to obtain the target product M23 of the present invention.

[0079] The value ranges of each material in Example 2 are listed as follows:

[0080]

[0081]

[0082] The chemical structural formula for generating the invention is shown as follows:

[0083] MAaBbCcDdEeFfM

[0084] Each group in the above formula represents the following respectively:

[0085] A is n-octylsiloxy The number of group units is 8.5, that is, a2 = 8.5, within the range of the invention design unit 1 - 15, the mass ratio is 7.50%, within the range of the design ratio 3 - 20%;

[0086] B is n-docosanyl to n-tetracosanyl siloxy Among them, R2 = 20 - 24, the number of group units is 8.5, that is, b2 = 8.5, within the range of the invention design unit 5 - 20, the mass ratio is 20%, within the range of the design ratio 25 - 50%;

[0087] C is the hydrosilylation structure of isooctyl methacrylate The number of group units is 3.8, that is, c2 = 3.8, within the range of the invention design unit 1 - 5, the mass ratio is 6.00%, within the range of the design ratio 1 - 10%;

[0088] D is phenylsiloxy The number of group units is 1, that is, d2 = 1, within the range of the invention design unit 1 - 10, the mass ratio is 1%, within the range of the design ratio 1 - 10%;

[0089] E represents a vinyl organosilicon group, and its structural form is The number of group units is 3.5, i.e., e2 = 3.5, within the range of 1 - 10 of the invention design unit, and the mass proportion is 3.5%, within the range of 1 - 10% of the design proportion.

[0090] F represents an aryl silicone group, and its structural form is The number of group units is 78, i.e., f2 = 78, within the range of 20 - 85 of the invention design unit, and the mass proportion is 50%. Example 3:

[0091] (1) Preparation of hydrogen-containing siloxane polymer:

[0092] Add 100 g of side-chain high-hydrogen polysiloxane (Dow Chemical Company, USA), 350 g of octamethylcyclotetrasiloxane (Dow Chemical Company, USA), and 5 g of hexamethyldisiloxane (Chengdu Guibao Technology Co., Ltd.) into a glass or stainless-steel reaction kettle with a strong stirring device. Stir and heat up to 80 - 90 °C, then add 8 g of acidic activated clay, keep the temperature constant, and continue the reaction process for 3 - 8 h. After the reaction is completed, remove the catalyst, pump the material into the low-boiling removal kettle, continuously stir during this process, heat to 110 - 130 °C, turn on the cooling circulating water, nitrogen, and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process lasts for 2 h to obtain the hydrogen-containing siloxane polymer M31 for use. This polymer is not taken out (only take a small amount when necessary for the determination of the -SiH group content);

[0093] (2) Preparation of long-chain alkane siloxane copolymer:

[0094] Perform dehydration pretreatment on long-chain olefin monomers, short-chain olefin monomers, and acrylate monomers respectively. The specific operation is as follows: Add the materials into a glass or stainless-steel reaction kettle with a strong electric stirring device, stir and heat to 100 - 110 °C, and perform vacuum dehydration for 1 - 1.5 h under the condition of -0.1 MPa, then cool down to 40 - 50 °C for use;

[0095] In the prepolymer M31 reaction kettle, put in the dehydrated various monomers. The quantities of each monomer are 120 g of long-chain olefin C 20 H 40 -C 24 H 48 (Shanghai Qicheng), 200 g of short-chain olefin C 12 H 24 (Shanghai Qicheng), and 50 g of lauryl methacrylate (Shandong Guohua Chemical). Stir and heat up to 80 °C, and introduce N 2,, then add an isopropanol dispersion of 0.3 g of platinum catalyst (dispersion concentration is 1%). During the reaction, the temperature of the system rises automatically, up to 150 °C at most. During this process, continuous stirring is carried out, and the reaction is kept at a constant temperature for 2 - 3 h. After the reaction is completed, turn on the cooling circulating water, nitrogen, and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process is continuously carried out under N₂ protection, and continuous vacuum distillation is carried out for 5 h to obtain the long-chain alkane siloxane copolymer M32.

[0096] In the reaction kettle of prepolymer M32, various monomers are put in. The amounts of each monomer are as follows: 75 g of vinyltriethoxysilane (Shandong Silicate), 35 g of phenyltriethoxysilane (Shandong Silicate), and 10 g of hydroxy-terminated silicone oil (Dow Chemical Company, USA). Stir and heat up to 80 °C, introduce N₂, and then add tetramethylammonium hydroxide. During the reaction, the system gradually becomes homogeneous, and the reaction is carried out at a constant temperature for 3 h. After the reaction is completed, turn on the heating, keep it at a constant temperature of 160 °C for 2 h. After that, turn on the cooling circulating water, nitrogen, and vacuum pump, and carry out vacuum distillation to remove the unreacted low-boiling substances. This process is continuously carried out under N₂ protection, and continuous vacuum distillation is carried out for 5 h to obtain the target product M33 of the present invention.

[0097] The value ranges of each material in Example 3 are listed as follows:

[0098]

[0099]

[0100] The chemical formula for generating the invention is shown as follows:

[0101] MAaBbCcDdEeFfM

[0102] Each group in the above formula represents the following respectively:

[0103] A is dodecylsiloxy The number of group units is 12.5, that is, a3 = 12.5, within the range of the invention design unit 1 - 15, and the mass ratio is 21.16%, within the range of the design ratio 10 - 30%;

[0104] B is n - eicosyl to n - tetracosylsiloxy Among them, R2 = 20 - 24, the number of group units is 5.1, that is, b3 = 5.1, within the range of the invention design unit 5 - 20, and the mass ratio is 12.7%, within the range of the design ratio 10 - 50%;

[0105] C is the hydrosilylation structure of lauryl methacrylate The number of group units is 2.5, that is, c3 = 2.5, within the range of the invention design unit 1 - 5, and the mass ratio is 5.29%, within the range of the design ratio 1 - 10%;

[0106] D is phenylsiloxy The number of group units is 3, that is, d3 = 3, within the range of 1 - 10 of the inventive design unit, with a mass percentage of 3.7%, within the range of 1 - 10% of the design ratio;

[0107] E represents a vinyl organosilicon group, and its structural form is The number of group units is 7, that is, e3 = 7, within the range of 1 - 10 of the inventive design unit, with a mass percentage of 7.94%, within the range of 1 - 10% of the design ratio.

[0108] F represents an aryl organosilicon group, and its structural form is The number of group units is 60, that is, f3 = 60, within the range of 20 - 85 of the inventive design unit, with a mass percentage of 38%.

[0109] The final inventive numbers of the above Examples 1, 2, and 3 are E1, E2, and E3 respectively. The proportion of different structures in each invention is shown in the following table:

[0110]

[0111] According to the general theory of "structure determines properties, and properties determine applications", the performance characteristics and applications of each invention represented by E1, E2, and E3 are:

[0112] The inventive product E1 and the corresponding competing products are added to the polyolefin plastic formula as auxiliaries in the same proportion to process into products. The filler in the formula accounts for 50%. The comparison of each performance index data is as follows in the table:

[0113] Project Blank E1 PE Wax <![CDATA[Product appearance 1 > 5 2 3 Machine Torque 100％ 72％ 90％ Elongation at Break 200 350 250 Surface Hydrophobic Angle 80° 100° 90° Coefficient of Dynamic Friction 0.5 0.38 0.42

[0114] Note 1: The appearance is ranked from excellent to poor as 1 - 5. 1 means the appearance is flat and moist, with good hand feeling; 5 means the appearance is rough, with a strong industrial plastic feeling. It is divided into five grades as the appearance evaluation.

[0115] In the practical application of the polyolefin plastic industry, the remarkable advantages of the inventive products can be summarized in the following table:

[0116]

[0117] Synthesis Example Invention E1 has a high relative proportion of alkyl groups and can effectively be compatible with various types of polyolefin plastic materials. During the plastic processing, when added in an amount of 0.5 - 1%, it can effectively reduce the internal stress during processing, reduce the torque, make the discharge more smooth, increase the production efficiency, reduce equipment wear and extend the service life. The mutual combination of the long-chain and short-chain olefins and the polyester structure of the invention can be reasonably distributed in the "crystalline region" and "amorphous region" of the plastic, having an obvious toughening effect on the plastic material and significantly enhancing the mechanical properties of the plastic. In the above case, compared with Invention E1, the structure of PE wax is single, with little room for product adjustment and a narrow application range. PE wax has a lower temperature resistance compared to Invention E1 and is prone to yellowing under high-temperature processing conditions, especially for light-colored products, which greatly affects the product application, while Invention E1 does not have this problem. Due to the presence of the "Si - O - Si" bond in the structure of Invention E1, compared with PE wax, it has strong molecular flexibility and high lubrication efficiency, so the addition amount is small, and it can minimize the impact of the additive on the various mechanical properties of the product system. In terms of the reduction ratio of torque, Invention E1 has a 20% higher efficiency compared to the competing products.

[0118] Add Invention E2 and the corresponding competing products as additives in the same proportion to the polyolefin plastic formula to process into products. The filler in the formula accounts for 50%. The data of each performance index is compared as follows in the table:

[0119] Project Blank E2 Silicone Masterbatch <![CDATA[Product appearance 1 > 5 1 2 Machine Torque 100％ 85％ 85％ Elongation at Break 200 300 300 Surface Hydrophobic Angle 80° 120° 90° Coefficient of Dynamic Friction 0.5 0.32 0.39

[0120] Note 1: The appearance is sorted from excellent to poor as 1 - 5. 1 means the appearance is flat and moist, with a good hand feeling; 5 means the appearance is rough, with a strong industrial plastic feeling. It is divided into five grades in this way as the appearance evaluation.

[0121] In the practical application of the polyolefin plastic industry, the remarkable advantages of the invention can be summarized in the following table:

[0122]

[0123] Synthesis Example Invention E2 has a relatively high proportion of siloxane segments compared to other inventions. It has strong molecular flexibility, high lubrication efficiency, and a relatively balanced proportion of siloxane segments and modified segments inside the molecule. It has good compatibility with resins, and the internal and external lubrication effects are balanced. During the processing, relying on the low surface tension of the siloxane, the invention can migrate quantitatively and directionally to the surface, improving the surface feel of the material, making it more moist and reducing the industrial feeling of the plastic, thus enhancing the product grade. At the same time, with the help of the action of unsaturated double bonds, the free radicals generated during the plastic processing can effectively combine with the double bonds, embedding the invention into the material and migrating without migrating out, so there will be no negative impact of oil bleeding and precipitation after the material is formed. In practical applications, when the addition amount is 0.5 - 1%, it can effectively improve the wear and scratch resistance of the product surface, and can also greatly enhance the moist feel of the product surface. Through the application evaluation and comparison of a plastic open mill, Invention E2 has obvious advantages over conventional silicone masterbatches in terms of the appearance state, feel lubrication, waterproof, anti-fouling, and scratch resistance of the obtained plastic products. In the above case, compared with Invention E2, the silicone masterbatch has too large a molecular weight, a very slow surface migration speed, and cannot completely cover the outer surface of the product, resulting in poor effects and efficiency in improving the surface hydrophobicity and feel of the product. During the processing of Invention E2, it can migrate quickly and directionally, and with the help of unsaturated bonds, it can be cured into the system during the material forming process, quickly and efficiently playing the role of improving the surface state and enhancing the product grade. It can be seen from the data in the above table that after adding Invention E2, the hydrophobic angle of the material can be effectively improved to 120°, and the effect can reach the level where water droplets do not remain on the product surface and directly slide off. The degree of moistness and fineness of the product surface is at a level that cannot be achieved by other competing products.

[0124] In the polyolefin plastic industry's practical application, Invention E3 and the corresponding competing products were added as additives to the polyolefin plastic formula in the same proportion to process products. The filler in the formula accounted for 50%. The data of each performance index is compared as follows in the table:

[0125] Project Blank E3 Silane Coupling Agent <![CDATA[Product appearance 1 > 5 3 4 Machine Torque 100％ 80％ 95％ Elongation at Break 200 280 220 Surface Hydrophobic Angle 80° 100° 85° Coefficient of Dynamic Friction 0.5 0.41 0.53

[0126] Note 1: The appearance is sorted from excellent to poor as 1 - 5. 1 means the appearance is flat and moist, with a good feel; 5 means the appearance is rough, with a strong industrial plastic feeling. It is divided into five grades in this way as the appearance evaluation.

[0127] In the practical application of the polyolefin plastic industry, the significant advantages of the invention can be summarized in the following table:

[0128]

[0129] Synthesis Example Invention E3 has a relatively balanced structure of polysiloxane and olefin, with an increased structure having a coupling function, which can effectively improve the binding force of the invention to various types of filler powders in the plastic formulation. This enables the invention to "firmly hold" the powders, and at the same time, with the help of the olefin structure in the molecule, it is fully dispersed into the plastic substrate. The presence of the polysiloxane structure effectively prevents the tendency of the well-dispersed powders to agglomerate again. During the actual application process, it can be used as an external lubricant and an internal release agent, which can effectively reduce the adhesion and friction of the resin to the metal surface, greatly reduce equipment wear, and improve production efficiency.

[0130] Synthesis Example Invention E3 has an increased proportion of hydrophilic polyether groups, which can improve the hydrophilic properties of traditional plastics. Due to the poor compatibility between the polyether structure and the plastic resin, and the low surface tension of the siloxane, this invention has a tendency to migrate to the surface inside the resin. To avoid the precipitation of this invention on the resin surface, the proportion of long-chain alkanes is increased in the structural design to balance its compatibility in the resin. In actual applications, when the addition amount is 0.5 - 1%, it can effectively increase the filling amount of the powder, help the powder to be effectively dispersed, prevent its agglomeration, and greatly reduce the impact of the filler on the mechanical properties of the material. In the above case, compared with Invention E3, the silane coupling agent has too high a reaction activity and too harsh storage and transportation conditions. At the same time, during the application process, there are a large number of problems of self-polymerization and self-crosslinking. On the one hand, it increases the ineffective usage amount of the additive, and it will also cause the problem of secondary agglomeration of the filler; on the other hand, the particles formed by self-polymerization are incompatible with the substrate, forming breakpoints to varying degrees, which greatly affects the mechanical properties of the material. Invention E3 does not have these defects. Through the application evaluation and comparison by a plastic open mill, compared with the conventional silane coupling agent, the plastic products obtained from Invention E3 have a more gentle and uniform appearance color, better mechanical properties of the products, and a larger powder addition amount under the premise of the same addition amount, making the products more cost-effective.

[0131] As described above, the provided implementation cases are one or more implementation manners provided in combination with specific contents, and it is not determined that the specific implementation of the present invention is only limited to these descriptions. Any approximation or similarity to the method, structure, etc. of the present invention, or several technical deductions or substitutions made under the premise of the inventive concept of the present invention, should be regarded as within the protection scope of the present invention.

Claims

1. A solvent-free branched siloxane multi-copolymer having the following molecular structural formula: MAaBbCcDdEeFfM Where: ① In the formula, M represents a silicone group, and its structural form is ② In the formula, A represents a short-chain alkyl silicone group, and its structural form is where R1 is a short-chain alkyl group, —C n H 2n+1, , where n = 8, 12, 14; ③ In the formula, B represents a long-chain alkyl silicone group, and its structural form is wherein R2 is a long-chain alkyl group, —C m H 2m+1, , where m = 20 - 24; In formula ④, C represents an ester hydrocarbon group organosilicon group, wherein R3 is an alkyl group, —C k H 2k+1 , where k = 4, 8, 12; D in formula (5) represents an aryl organosilicon group, and its structural form is E in formula ⑥ represents an organosilicon structural group containing a vinyl unsaturated bond, and the structural form is; In formula (VII), F represents an aryl organosilicon group, and its structural form is In formula ⑧, a, b, c, d, e, and f are the relative quantities of each unit group within the molecule of the invention, and the calculated values are retained to one decimal place, where: a＝1-15； b＝5-20； c＝1-5； d＝1-10； e＝1-10； f＝20-85。 2. The branched silicone copolymer according to claim 1, characterized in that: The B group is obtained by hydrosilylation reaction from the following raw materials: C n H 2n , where n = 20 - 24.

3. The branched siloxane copolymer according to claim 1, characterized in that: The C group is obtained by hydrosilylation reaction of methacrylate esters with the following structures: butyl methacrylate, isooctyl methacrylate, lauryl methacrylate.

4. The branched siloxane copolymer according to claim 1, characterized in that: The D group is obtained by polymerization reaction of an organosilicon monomer with the following structure and an intermediate product: Or 5. The branched siloxane copolymer according to claim 1, wherein: The E group is obtained by polymerization reaction of an organosilicon monomer with the following structure and an intermediate product: or 6. The branched silicone copolymer according to claim 1, wherein: The F structural unit is block copolymerized on the main chain of the entire long-chain alkane siloxane copolymer molecule, and the molar unit number ratio of the F structural unit in the entire long-chain alkane siloxane copolymer molecule is 20 - 85%.

7. The branched siloxane copolymer according to claim 1 or 2, wherein: The B structural unit is a side-chain modified structural unit of the entire long-chain alkane siloxane copolymer molecule, and the molar unit number ratio of the B structural unit in the entire long-chain alkane siloxane copolymer molecule is 5 - 20%.

8. The branched silicone copolymer according to claim 1 or 4, wherein: The D structural unit is block copolymerized on the main chain of the entire long-chain alkane siloxane copolymer molecule, and the molar unit number ratio of the D structural unit in the entire long-chain alkane siloxane copolymer molecule is 1 - 10%.

9. The branched siloxane copolymer according to claim 1 or 5, characterized in that: The E structural unit is block copolymerized on the main chain of the entire long-chain alkane siloxane copolymer molecule, and the molar unit number ratio of the E structural unit in the entire long-chain alkane siloxane copolymer molecule is 1 - 10%.

10. A preparation method of the branched siloxane multi-copolymer according to any one of claims 1 - 9, the preparation method comprising the following steps: (1) Preparation of a hydrogen-containing siloxane polymer: Add 45 g of a side-chain high-hydrogen-content polysiloxane containing Si-H structure, 153 g of octamethylcyclotetrasiloxane, and 2 g of hexamethyldisiloxane into a glass or stainless steel reaction kettle equipped with a strong stirring device, stir and heat up to 80 - 90 °C, then add a catalyst accounting for 0.3% of the total mass in the kettle, keep the temperature constant, and continuously react for 5 h. After the reaction, remove the catalyst, pump the material into a de-low kettle, continuously stir during this process, heat to 120 °C, turn on the cooling circulating water, nitrogen, and vacuum pump, and perform vacuum distillation to remove unreacted low-boiling substances. This process lasts for 2 h to obtain a hydrogen-containing siloxane polymer M1; (2) Preparation of a long-chain alkyl ester group-containing siloxane copolymer: Perform dehydration pretreatment on the long-chain olefin monomer, short-chain olefin monomer, and acrylate monomer respectively. The specific operation is: add the material into a glass or stainless steel reaction kettle equipped with a strong electric stirring device, stir and heat to 100 - 110 °C, and perform vacuum dehydration for 1 - 1.5 h under the condition of -0.1 MPa, then cool down to 40 - 50 °C for standby; Add 150 g of a hydrogen-containing siloxane polymer M1 with Si-H structure into a glass or stainless-steel reactor equipped with a powerful stirring device. Add various monomers that have been dehydrated. The total molar amount of various monomers is 0.6 mol. Stir and heat up to 90 - 100 °C, and pass N 2, , and then add an ethanol dispersion of an organoplatinum catalyst accounting for 0.03% of the total mass in the reactor. During the reaction process, the temperature of the system automatically rises to a maximum of 130 - 150 °C. During this process, continuously stir and keep the temperature for reaction for 2 - 3 h. After the reaction is completed, turn on the cooling circulating water, nitrogen, and vacuum pump, and keep the temperature at 160 °C for vacuum distillation to remove unreacted low-boiling substances. This process is continuously carried out under N2 protection, and vacuum distillation is continuously carried out for 2 h to obtain a long-chain alkane siloxane copolymer M2; (3) Preparation of a multi-modified siloxane copolymer: Take 100 g of the long-chain alkyl ester group-structured silicone copolymer M2 obtained in the step (2), 8 g of the structure CH2=CHSi(OEt)3 and 3 g of the structure PhSi(OEt)3, continuously stir, add an appropriate amount of catalyst, slowly heat up to 80 - 100 °C while stirring, react at a constant temperature for 3 h, the viscosity of the system starts to change, and the whole system starts to be transparent and homogeneous. After the system is stable, add a neutralizing reagent to the reaction vessel, remove the catalyst and continuously stir for 1 h. After the reaction is completed, heat up to 180 °C and connect a condensing device, turn on the vacuum, and carry out vacuum distillation for 3 h to distill out the low-boiling substances in the system, then the branched silicone multi-copolymer M3 can be obtained.

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