Silicon-containing composition for processing chlorine-containing polyolefin material and preparation method thereof

Abstract

The invention relates to the technical field of material processing, and discloses a silicon-containing composition for processing a chlorine-containing polyolefin material and a preparation method, which are used for solving the problems of processing and extrusion of the chlorine-containing polyolefin composite material. The invention relates to a silicon-containing composition for processing a chlorine-containing polyolefin material. The silicon-containing composition comprises 5-95 parts of modified polysiloxane, 5-95 parts of hydrocarbon wax, 5-95 parts of fatty acid amide, 5-95 parts of metallic soap and 1-5 parts of other auxiliaries. The silicon-containing composition for processing the chlorine-containing polyolefin material is applied to processing and extrusion of the chlorine-containing polyolefin composite material, modified polysiloxane not only contains a plastic-loving part but also contains a filler-loving part, and meanwhile, the whole molecular structure takes organic silicon as a main chain, so that the special performance of the organic silicon is achieved; according to the present invention, the chlorine-containing polyolefin composite material is compounded with other lubricants so as to achieve efficient internal and external lubrication, high cost performance and no precipitation, can effectively delay the decomposition time of the chlorine-containing polyolefin, can weaken the adhesion effect between the chlorine-containing polyolefin and the metal, can substantially prolong the screw cleaning time during the processing of the chlorine-containing polyolefin composite material, and can improve the production efficiency.

Description

Technical Field

[0001] The invention relates to the technical field of material processing, in particular to a silicon-containing composition for processing chlorine-containing polyolefin materials and a preparation method thereof. Background Art

[0002] For a long time, chlorinated polyolefin materials (such as PVC, CPVC, PVDC, etc.) have been widely used in people's production and life. In the global plastics field, the production capacity and consumption capacity of chlorinated polyolefin materials have always been at the forefront of all general plastics; chlorinated polyolefins are often used in wires and cables, daily necessities, home decoration, construction, infrastructure and other fields due to their excellent properties, such as corrosion resistance, flame retardancy, chemical resistance, and easy processing. However, chlorinated polyolefins are unstable and easily thermally decomposed or oxidized. Therefore, in the processing of chlorinated polyolefin materials, it is particularly important to add lubricants and heat stabilizers. Among them, polyvinyl chloride (PVC) is often added with a large amount of fillers when used, which will greatly affect its processing performance. In addition, after the degradation of PVC, the screw adhesion ability will be enhanced, and the surface of the extruded parts will be rough and defective, thereby reducing production efficiency and product qualification rate.

[0003] In the existing chlorinated polyolefin material formulations, hydrocarbon waxes, fatty acids, fatty acid esters, etc. are generally used as processing lubricants. These lubricants have general lubrication efficiency and are added in large amounts. They do not have much effect on delaying the degradation of chlorinated polyolefins, and they cannot improve the problem of chlorinated polyolefins sticking to the screw after degradation.

[0004] Chlorinated polyolefin lubricants have been reported in the literature, and most of them are small molecule waxes such as small molecule hydrocarbon waxes, fatty acids, fatty acid esters, metal soaps and fatty amides and their composites as lubricants. For example, the patent with publication number CN107573618A discloses a method for preparing a PVC lubricant, which obtains a PVC lubricant by mixing mineral oil, pure cashew oleoresin, triolein, hydrogenated vegetable oil, lemon essential oil, cypress essential oil, and cetearyl alcohol. This kind of lubrication effect is general, suitable for transparent PVC materials, and cannot solve the problem of PVC degradation and sticking to the screw.

[0005] For example, the patent with publication number CN110713671A discloses a lubricant for PVC processing, which is prepared by mixing mineral oil, white oil, higher fatty acid barium, fumaric acid, dipropylene glycol, and cetearyl alcohol. This lubricant has the risk of small molecule precipitation, and the reaction structure is difficult to control.

[0006] For example, the patent with publication number CN103571586A discloses a PVC lubricant, which is prepared by mixing stearic acid, glycerol, emulsifier and phosphoric acid. This lubricant has a general lubricating effect and has the risk of small molecule precipitation.

[0007] For example, the patent with publication number CN105396659A discloses a method for preparing a PVC lubricant, which comprises mixing hydroxystearic acid solid, phosphoric acid liquid, octadecyl alcohol liquid and adipic acid liquid in a ball mill for reaction to prepare the PVC lubricant. The structure of this lubricant is difficult to control, the lubrication effect is not efficient enough, and the problem of PVC degradation and sticking to the screw cannot be solved.

[0008] For example, the patent with publication number CN110698599A discloses a highly efficient and environmentally friendly PVC lubricant and a preparation method thereof, wherein fatty acids, metal soaps, carboxylates, fatty amides, fatty alcohols, hydrocarbon waxes, epoxy soybean oils, phosphites, polytetrafluoroethylene waxes, and coupling agents are melted and mixed uniformly, and the mixture is reacted with a peroxide crosslinking agent and maleic anhydride to obtain the PVC lubricant. The structure of this lubricant is difficult to control, and the lubrication effect is average.

[0009] For example, the patent with publication number CN103897293A discloses an internal lubricant, which is obtained by reacting stearyl alcohol, fumaric acid and trimethylolpropane. This lubricant cannot solve the problem of PVC degradation and sticking to the screw.

[0010] For example, the patent with publication number CN101578356A discloses a multi-component lubricant composition for processing rigid vinyl chloride polymers, wherein the lubricant composition is prepared by mixing oxidized hydrocarbon wax and metal salt. This lubricant has a general lubricating effect and requires a large amount of lubricant. Summary of the invention

[0011] Technical problems solved by the present invention:

[0012] The present invention is used to improve the processing lubrication of chlorinated polyolefin composite materials, which can make the compatibility of filler particles and chlorinated polyolefin resins better and can delay the degradation of chlorinated polyolefins, thereby solving the problem of adhesion of chlorinated polyolefins to the screw after degradation, thereby further improving product production efficiency and product qualification rate.

[0013] The technical solution adopted by the present invention is:

[0014] In view of the above-mentioned technical problems, the object of the present invention is to provide a silicon-containing composition for processing chlorine-containing polyolefin materials and a preparation method thereof.

[0015] The silicon-containing composition for processing chlorinated polyolefins provided by the present invention is obtained by compounding modified polysiloxane with a variety of wax lubricants. The compounded lubricant has a lower production cost and can achieve excellent internal and external lubrication effects. Among them, we use the modified polysiloxane molecular structure that contains both a part compatible with the chlorinated polyolefin resin and a polar group that reacts with fillers (inorganic fillers, such as calcium carbonate, talcum powder, diatomaceous earth, titanium dioxide and other fillers), which associates with the filler particles, thereby achieving a volume expansion effect for the filler and the chlorinated polyolefin. In addition, the presence of the alkyl segment in the modified polysiloxane makes the modified polysiloxane have an excellent lubricating effect. In the present invention, the modified polysiloxane can make the filler fully dispersed in the chlorine-containing polyolefin resin, and can effectively increase the mechanical properties of the chlorine-containing polyolefin composite material; and can be compounded with other lubricants to achieve both internal and external lubrication, high cost performance, no precipitation, excellent processing lubrication and product extrusion appearance without defects, and can delay the degradation of the chlorine-containing polyolefin; the modified polysiloxane molecule contains a non-polar long carbon chain structure, can have good compatibility with other waxes, and can reduce the precipitation of other waxes; the polar groups in the modified polysiloxane and the polysiloxane can react with the metal atoms on the surface of the metal screw to form a protective film, improve the adhesion problem of the chlorine-containing polyolefin to the screw after degradation, and improve the product production efficiency and product qualification rate.

[0016] The invention adopts modified polysiloxane to compound with other lubricants to prepare a high-performance, low-cost mixed lubricant. The modified polysiloxane contains both a plastic-affinity part and a filler-affinity part, and has a good volume expansion effect. At the same time, the entire molecular structure has organic silicon as the main chain and has the special properties of organic silicon. It is compounded with other lubricants to achieve both internal and external lubrication, high cost performance, no precipitation, excellent processing lubrication and product extrusion appearance without defects, and delays the degradation of chlorinated polyolefins. Moreover, the polar groups in the modified polysiloxane and the polysiloxane can react with the metal atoms on the surface of the metal screw to form a protective film, thereby improving the adhesion problem of the chlorinated polyolefin to the screw after degradation, and improving the product production efficiency and product qualification rate.

[0017] The specific contents are as follows:

[0018] First, the present invention provides a silicon-containing composition for processing chlorine-containing polyolefin materials, wherein the components, by weight, include 5 to 95 parts of modified polysiloxane, 5 to 95 parts of hydrocarbon wax, 5 to 95 parts of fatty amide, 5 to 95 parts of metal soap, and 1 to 5 parts of other additives.

[0019] According to some preferred embodiments, in the aforementioned silicon-containing composition, each component, by weight, includes 10 to 95 parts of modified polysiloxane, 10 to 95 parts of hydrocarbon wax, 10 to 95 parts of fatty amide, 10 to 95 parts of metal soap, and 1 to 5 parts of other additives.

[0020] According to some preferred embodiments, the hydrocarbon wax includes at least one of polyethylene wax, chlorinated polyethylene wax, oxidized polyethylene wax, oxidized chlorinated polyethylene wax, polypropylene wax, chlorinated polypropylene wax, oxidized polypropylene wax, oxidized chlorinated polypropylene wax, paraffin wax, Fischer-Tropsch wax, and montan wax.

[0021] According to some preferred embodiments, the fatty amide includes at least one of erucamide, oleamide, stearamide, ethylene bisstearamide, ethylene bisoleamide, and octadecyl erucamide.

[0022] According to some preferred embodiments, the metal soap includes at least one of lead stearate, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, sodium stearate, lithium stearate, lead oleate, zinc oleate, calcium oleate, sodium oleate, and lead erucate.

[0023] According to some preferred embodiments, other additives include at least one of an antioxidant, an antistatic agent, an anti-ultraviolet agent, and an antibacterial agent. Specifically,

[0024] The antioxidant includes at least one of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) isooctyl acrylate, N-phenyl-α-naphthylamine, alkyl phenothiazine, benzotriazole, mercaptobenzothiazole, 2,6-di-tert-butyl-p-cresol, N-cyclohexyl-N'-phenyl-p-phenylenediamine, triphenyl phosphite, diphenyl-isooctyl phosphite, and tributyl phosphite.

[0025] The anti-ultraviolet agent includes at least one of phenyl o-hydroxybenzoate, 2,2',4,4'-tetrahydroxybenzophenone, and 2-(2, hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole.

[0026] The antibacterial agent includes at least one of silver ion antibacterial agent, zinc oxide, copper oxide, ammonium dihydrogen phosphate, lithium carbonate, sodium pentachlorophenol, p-nitrophenol, glutaraldehyde and ethylene glycol methyl ether.

[0027] The antistatic agent includes at least one of stearic acid trimethyl ammonium chloride, stearic acid dimethyl amyl ammonium chloride, alkyl tertiary amine sodium nitrate, trihydroxyethyl methyl quaternary ammonium sodium sulfate, N,N-hexadecylethyl morpholine sodium sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium polyacrylate, and sodium polystyrene sulfonate.

[0028] According to some preferred embodiments, the structural formula of the modified polysiloxane is shown in (1):

[0029]

[0030] R 7 , R 8 , R 18, R 19 , R 20 , R 21 are each independently a monovalent organic group or atom;

[0031] n is an integer greater than 1;

[0032] R 7 , R 8 , R 18 , R 19 , R 20 , R 21 The structures are each independently selected from one of the general formulae (1-1) to (1-4):

[0033] ——C a H (2a+1) (1-1)

[0034] ——C b H (2b-1) (1-2)

[0035]

[0036] a is an integer greater than 0;

[0037] b is an integer greater than 1;

[0038] R 1 The structure is selected from the general formula (1-1) or (1-2);

[0039] R 2 , R 3 , R 4 , R 5 The structures of are independently selected from the general formula (1-1) or (1-2); R 2 , R 3 , R 4 , R 5 In the structure, there is at least one A, A is as shown in the general formula (1-1) and a>8;

[0040] R 10 , R 11 , R 12 , R 13 , R 14 The structures of are each independently selected from one of the general formulae (1-1) to (1-3) and (1-5):

[0041]

[0042] R 10 , R 11 , R 12 , R 13There is at least one B, B is as shown in general formula (1-3);

[0043] R 6 , R 9 , R 15 As shown in general formula (1-6),

[0044] -C c H 2c - (1-6)

[0045] c is an integer greater than 1;

[0046] R 16 is one of hydrogen atom, alkyl group, halogenated alkyl group and alkyl group containing polar group; among alkyl group, halogenated alkyl group and alkyl group containing polar group, the number of carbon atoms is an integer of 10 to 100; the polar group containing polar group is one of amino group, imide group, alkyl group, alkoxy group, epoxy alkoxy group, carboxylic acid alkoxy group, hydroxyl group, ester group and halogen atom;

[0047] R 17 It is one of a hydrogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, an epoxyalkoxy group, a carboxylic acid alkoxy group, a hydroxyl group, and a halogen atom; in the alkyl group, the alkoxy group, the epoxyalkoxy group, and the carboxylic acid alkoxy group, the number of carbon atoms is an integer greater than 1.

[0048] According to some preferred embodiments, the substituent R 16 In the above, the polar group is one of an amino group, an amide group, an alkoxy group, an epoxyalkoxy group, a carboxylic acid alkoxy group, a hydroxyl group, and a halogen atom.

[0049] According to some preferred embodiments, the inorganic filler includes at least one of calcium carbonate, mica powder, talc, montmorillonite, wollastonite powder, aluminum hydroxide, magnesium hydroxide, glass microbeads, kaolin, barium sulfate, titanium dioxide, silicon dioxide, and spherical silicon micropowder.

[0050] According to some preferred embodiments, the preparation method of the modified polysiloxane is prepared by the following steps:

[0051] Step 1: Prepare alkyl-containing cyclosiloxane, and obtain single-terminal hydrogen-containing polysiloxane through ring-opening polymerization;

[0052] Step 2: Prepare a cyclosiloxane containing a polar functional group, and obtain a single-terminal hydrogen-containing polysiloxane through ring-opening polymerization;

[0053] Step 3: Mixing the alkyl-containing single-terminal hydrogen-containing polysiloxane, the polar functional group-containing single-terminal hydrogen-containing polysiloxane and the vinyl-containing polysiloxane to obtain a modified polysiloxane through a catalytic reaction.

[0054] According to some preferred embodiments, the structure of the alkyl-containing cyclosiloxane is shown in general formula (2):

[0055]

[0056] R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 are each independently a monovalent organic group or a hydrogen atom; the structure of the monovalent organic group is the general formula (1-1) or (1-2);

[0057] R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 In the structure, there is at least one A, A is as shown in the general formula (1-1) and a>8.

[0058] According to some preferred embodiments, the structure of the cyclosiloxane containing polar functional groups is shown in general formula (3):

[0059]

[0060] R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 are each independently a monovalent organic group or a hydrogen atom; the structure of the monovalent organic group is the general formula (1-3);

[0061] R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 In the structure, there is at least one B, and B is as shown in the general formula (1-3).

[0062] According to some preferred embodiments, in step 1 and step 2, the catalyst for the ring-opening polymerization includes one or more of sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, tetramethylammonium hydroxide, and tetrabutylammonium hydroxide.

[0063] According to some preferred embodiments, in step 1 and step 2, the temperature range of the ring-opening polymerization is 100-200°C.

[0064] According to some preferred embodiments, in step 1 and step 2, the amount of catalyst used in the ring-opening polymerization is 0.1-2% of the total mass of the reaction materials.

[0065] According to some preferred embodiments, in step 3, the weight average molecular weight of the vinyl-containing polysiloxane is in the range of 1,000-1,000,000.

[0066] According to some preferred embodiments, in step three, the catalyst is a platinum catalyst.

[0067] According to some preferred embodiments, in step three, the catalytic reaction temperature is 70-200°C.

[0068] According to some preferred embodiments, in step 3, the amount of catalyst used is 0.1-2% of the total mass of the reactants.

[0069] According to some preferred embodiments, in step three, the reaction molar ratio of the alkyl-containing single-terminal hydrogen-containing polysiloxane, the polar functional group-containing single-terminal hydrogen-containing polysiloxane, and the vinyl-containing polysiloxane is 10-99:10-99:1-99.

[0070] According to some preferred embodiments, the alkyl-containing cyclosiloxane has the following characteristics:

[0071] The alkyl-containing cyclosiloxane is prepared by catalytic reaction of hydrogen-containing cyclosiloxane and unsaturated alkane;

[0072] The catalyst for preparing the alkyl-containing cyclosiloxane is a platinum catalyst;

[0073] The preparation temperature of the alkyl-containing cyclosiloxane is 70 to 200°C;

[0074] The amount of catalyst used in the preparation of alkyl-containing cyclosiloxane is 0.1-2% of the total mass of the reaction material;

[0075] The molar ratio of hydrogen-containing cyclosiloxane to unsaturated alkane is 1:1 to 4;

[0076] The hydrogen-containing cyclosiloxane may be tetramethylcyclotetrasiloxane;

[0077] Unsaturated alkanes are alkenes having unsaturated double bonds.

[0078] According to some preferred embodiments, the cyclosiloxane containing polar functional groups has the following characteristics:

[0079] The structure of the cyclosiloxane containing polar functional groups is shown in the general formula (3):

[0080]

[0081] R30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 are each independently a monovalent organic group or a hydrogen atom; the structure of the monovalent organic group is the general formula (1-3);

[0082] R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 In the structure, there is at least one B, and B is as shown in the general formula (1-3);

[0083] The polar functional group-containing cyclosiloxane is prepared by catalytic reaction of vinyl-containing cyclosiloxane and polar functional group-containing alkane;

[0084] The catalyst for preparing the cyclosiloxane containing polar functional groups is one of sodium ethoxide, sodium hydride, tetramethylammonium hydroxide and tetrabutylammonium hydroxide;

[0085] The preparation temperature of the cyclosiloxane containing polar functional groups is 90 to 150°C;

[0086] The amount of catalyst used in the preparation of cyclosiloxane containing polar functional groups is 0.1-2% of the total mass of the reaction substances;

[0087] The catalyst for preparing the cyclosiloxane containing polar functional groups is diluted with a diluent before use, and the diluent includes at least one of methanol, ethanol, isopropanol, and cyclohexane;

[0088] The molar ratio of vinyl-containing cyclosiloxane to polar functional group-containing alkane is 1:1 to 4;

[0089] The vinyl-containing cyclosiloxane includes at least one of tetramethyltetravinylcyclotetrasiloxane, octavinylcyclotetrasiloxane, hexavinylcyclotrisiloxane, trimethyltrivinylcyclotrisiloxane, hexamethyldivinylcyclotetrasiloxane, tetraphenyltetravinylcyclotetrasiloxane, diphenylhexavinylcyclotetrasiloxane and triphenyltrivinylcyclotrisiloxane;

[0090] The structural formula of the alkane containing polar functional groups is shown in the general formula (1-7):

[0091]

[0092] X is a hydrogen atom, a halogen atom, or any one of the general formula (1-1) and the general formula (1-2).

[0093] According to some preferred embodiments, the ultra-high molecular weight polysiloxane has the following characteristics:

[0094] The structure of ultra-high molecular weight polysiloxane is shown in general formula (4):

[0095]

[0096] R1 and R2 are each independently a monovalent organic group or atom; x is an integer greater than 1000;

[0097] R1 and R2 are one or more of methyl, ethyl, phenyl, hydroxyl, vinyl, hydrogen atom, and long-chain alkyl with carbon number greater than 8; the long-chain alkyl can be any straight-chain alkyl or branched-chain alkyl.

[0098] Second, the present invention provides a method for preparing the aforementioned silicon-containing composition for processing chlorine-containing polyolefin materials, comprising the following steps:

[0099] S1 modified polysiloxane, hydrocarbon wax, fatty amide, metal soap and other additives are blended at high temperature to obtain a mixed material;

[0100] The S2 mixed material is granulated by droplet granulation to obtain a silicon-containing composition for processing chlorine-containing polyolefin materials.

[0101] The beneficial effects achieved by the present invention are:

[0102] The silicon-containing composition for processing chlorine-containing polyolefin materials provided in the present application has:

[0103] (1) It has excellent lubrication effect when used in chlorinated polyolefin composite materials;

[0104] (2) The modified polysiloxane can fully disperse the filler in the chlorinated polyolefin resin, which can effectively increase the mechanical properties of the chlorinated polyolefin composite material;

[0105] (3) Compounding modified polysiloxane with other waxes can effectively combine the properties of modified polysiloxane and other waxes, so that the mixed lubricant has both internal and external lubrication effects and has a lower price. It has excellent performance in the processing and extrusion of chlorinated polyolefin composites.

[0106] (4) Modified polysiloxane also has good compatibility with other waxes and can reduce the precipitation of other waxes;

[0107] (5) Effectively delay the degradation of chlorinated polyolefin materials;

[0108] (6) The polar groups in the modified polysiloxane and the polysiloxane can react with the metal screw to form a protective film, which improves the adhesion problem of the chlorinated polyolefin to the screw after degradation, and improves the production efficiency and product qualification rate of the product;

[0109] (7) The preparation of masterbatch is simple, environmentally friendly and low-cost. DETAILED DESCRIPTION

[0110] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0111] Example 1

[0112] This embodiment provides a method for preparing a silicon-containing composition for processing chlorine-containing polyolefin materials. The components of the silicon-containing composition are as follows:

[0113] Modified polysiloxane 1:30 parts

[0114] Polyethylene wax: 30 parts

[0115] Erucic acid amide: 30 parts

[0116] Zinc stearate: 8 parts

[0117] Benzotriazole: 1 part

[0118] Ammonium dihydrogen phosphate: 1 part

[0119] Modified polysiloxane, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulated to obtain a silicon-containing composition 1 for processing chlorine-containing polyolefin materials.

[0120] The modified polysiloxane 1 has the following structure:

[0121]

[0122] The preparation method of modified polysiloxane 1 is as follows:

[0123] Step 1: add α-dodecene and tetramethylcyclotetrasiloxane in a molar ratio of 4:1 to a flask, stir at 60°C for 1h, slowly drop 0.1% of the total mass of chloroplatinic acid catalyst of α-dodecene and tetramethylcyclotetrasiloxane after stirring evenly, and continue stirring and reacting for 8h; after the reaction is completed, increase the temperature to 150°C, add 0.2% of the total mass of α-dodecene and tetramethylcyclotetrasiloxane tetramethylammonium hydroxide, stir and mix for 1h, then add monohydrogenated double-capped siloxane, and continue stirring and reacting for 8h, and after the reaction is completed, increase the temperature to 180°C and decompress for 2h to obtain an alkyl-modified single-terminal hydrogenated polysiloxane A1 with 16 polymer segments;

[0124] Step 2: Add butyl acetate and tetramethyltetravinylcyclotetrasiloxane in a molar ratio of 4:1 into a flask, stir at 85°C for 1 hour, slowly drop a 20wt% tetramethylammonium hydroxide ethanol solution (0.5% of the total mass of butyl acetate and tetramethyltetravinylcyclotetrasiloxane) into the flask, stir evenly at 85°C, heat to 150°C and stir for 18 hours, then add monohydrogenated double-capped siloxane, continue stirring for 8 hours, and after the reaction is complete, raise the temperature to 180°C and decompress for 2 hours to obtain a polar group-modified single-terminal hydrogenated polysiloxane B1 with 16 polymer segments;

[0125] Step 3: Add A1, B1 and vinyl polysiloxane with a polymer chain length of 40 in a molar ratio of 1:1:1 into a flask and stir at 85°C for 1 hour. After stirring evenly, slowly drop A1, B1 and 0.1% of the total mass of vinyl polysiloxane into a chloroplatinic acid catalyst, and continue stirring the reaction for 8 hours to obtain the modified polysiloxane additive 1.

[0126] Example 2

[0127] This embodiment provides a silicon-containing composition for processing chlorine-containing polyolefin materials and a preparation method thereof. The components of the silicon-containing composition are as follows:

[0128] Modified polysiloxane 1:40 parts

[0129] Polyethylene wax: 30 parts

[0130] Erucic acid amide: 20 parts

[0131] Zinc stearate: 8 parts

[0132] Benzotriazole: 1 part

[0133] Ammonium dihydrogen phosphate: 1 part

[0134] Modified polysiloxane, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 2 for processing chlorine-containing polyolefin materials.

[0135] The structure and preparation method of modified polysiloxane 1 are the same as those in Example 1.

[0136] Example 3

[0137] This embodiment adopts a method for preparing a silicon-containing composition for processing chlorine-containing polyolefin materials. The components of the silicon-containing composition are as follows:

[0138] Modified polysiloxane 1:50 parts

[0139] Polyethylene wax: 30 parts

[0140] Erucic acid amide: 10 parts

[0141] Zinc stearate: 8 parts

[0142] Benzotriazole: 1 part

[0143] Ammonium dihydrogen phosphate: 1 part

[0144] Modified polysiloxane, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 3 for processing chlorine-containing polyolefin materials.

[0145] The structure and preparation method of modified polysiloxane 1 are the same as those in Example 1.

[0146] Example 4

[0147] This embodiment provides a silicon-containing composition for processing chlorine-containing polyolefin materials and a preparation method thereof. The components of the silicon-containing composition are as follows:

[0148] Modified polysiloxane 2: 30 parts

[0149] Polyethylene wax: 30 parts

[0150] Erucic acid amide: 30 parts

[0151] Zinc stearate: 8 parts

[0152] Benzotriazole: 1 part

[0153] Ammonium dihydrogen phosphate: 1 part

[0154] Modified polysiloxane, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 4 for processing chlorine-containing polyolefin materials.

[0155] The modified polysiloxane 2 has the following structure:

[0156]

[0157] The preparation method of modified polysiloxane 2 is as follows:

[0158] Step 1: Add α-dodecene and tetramethylcyclotetrasiloxane in a molar ratio of 4:1 to a flask, stir at 60°C for 1h, slowly drop 0.1% of the total mass of chloroplatinic acid catalyst of α-dodecene and tetramethylcyclotetrasiloxane after stirring evenly, and continue stirring and reacting for 8h; after the reaction is completed, increase the temperature to 150°C, add 0.2% of the total mass of α-dodecene and tetramethylcyclotetrasiloxane tetramethylammonium hydroxide, stir and mix for 1h, then add monohydrogenated double-capped siloxane, and continue stirring and reacting for 8h. After the reaction is completed, increase the temperature to 180°C and decompress for 2h to obtain an alkyl-modified single-terminal hydrogenated polysiloxane A1 with 16 polymer segments;

[0159] Step 2: Add butyl acetate and tetramethyltetravinylcyclotetrasiloxane in a molar ratio of 4:1 into a flask, stir at 85°C for 1 hour, slowly drop a 20wt% tetramethylammonium hydroxide ethanol solution (0.5% of the total mass of butyl acetate and tetramethyltetravinylcyclotetrasiloxane) into the flask, stir evenly at 85°C, heat to 150°C and stir for 18 hours, then add monohydrogenated double-capped siloxane, continue stirring for 8 hours, and after the reaction is complete, raise the temperature to 180°C and decompress for 2 hours to obtain a polar group-modified single-terminal hydrogenated polysiloxane B1 with 16 polymer segments;

[0160] Step 3: Add A1, B1 and vinyl polysiloxane with a polymer chain length of 80 in a molar ratio of 1:1:1 into a flask and stir at 85°C for 1 hour. After stirring evenly, slowly drop A1, B1 and 0.1% of the total mass of vinyl polysiloxane into a chloroplatinic acid catalyst, and continue stirring the reaction for 8 hours to obtain the modified polysiloxane additive 2.

[0161] Example 5

[0162] This embodiment provides a method for preparing a silicon-containing composition for processing chlorine-containing polyolefin materials. The components of the silicon-containing composition are as follows:

[0163] Modified polysiloxane 2: 40 parts

[0164] Polyethylene wax: 30 parts

[0165] Erucic acid amide: 20 parts

[0166] Zinc stearate: 8 parts

[0167] Benzotriazole: 1 part

[0168] Ammonium dihydrogen phosphate: 1 part

[0169] Modified polysiloxane, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 5 for processing chlorine-containing polyolefin materials.

[0170] The structure and preparation method of modified polysiloxane 2 are the same as those in Example 4.

[0171] Example 6

[0172] This embodiment provides a method for preparing a silicon-containing composition for processing chlorine-containing polyolefin materials. The components of the silicon-containing composition are as follows:

[0173] Modified polysiloxane 2: 50 parts

[0174] Polyethylene wax: 30 parts

[0175] Erucic acid amide: 10 parts

[0176] Zinc stearate: 8 parts

[0177] Benzotriazole: 1 part

[0178] Ammonium dihydrogen phosphate: 1 part

[0179] Modified polysiloxane, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 6 for processing chlorine-containing polyolefin materials.

[0180] The structure and preparation method of modified polysiloxane 2 are the same as those in Example 4.

[0181] Comparative Example 1

[0182] The modified polysiloxane is replaced by dimethyl silicone oil having a polymer chain length of 40 to prepare a silicon-containing composition for processing chlorinated polyolefin materials. The components of the composition are as follows:

[0183] Dimethyl silicone oil: 30 parts

[0184] Polyethylene wax: 30 parts

[0185] Erucic acid amide: 30 parts

[0186] Zinc stearate: 8 parts

[0187] Benzotriazole: 1 part

[0188] Ammonium dihydrogen phosphate: 1 part

[0189] Dimethyl silicone oil, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 7 for processing chlorine-containing polyolefin materials.

[0190] Comparative Example 2

[0191] The modified polysiloxane is replaced by dimethyl silicone oil having a polymer chain length of 40 to prepare a silicon-containing composition for processing chlorinated polyolefin materials. The components of the composition are as follows:

[0192] Dimethyl silicone oil: 40 parts

[0193] Polyethylene wax: 30 parts

[0194] Erucic acid amide: 20 parts

[0195] Zinc stearate: 8 parts

[0196] Benzotriazole: 1 part

[0197] Ammonium dihydrogen phosphate: 1 part

[0198] Dimethyl silicone oil, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 8 for processing chlorine-containing polyolefin materials.

[0199] Comparative Example 3

[0200] The modified polysiloxane is replaced by dimethyl silicone oil having a polymer chain length of 40 to prepare a silicon-containing composition for processing chlorinated polyolefin materials. The components of the composition are as follows:

[0201] Dimethyl silicone oil: 50 parts

[0202] Polyethylene wax: 30 parts

[0203] Erucic acid amide: 10 parts

[0204] Zinc stearate: 8 parts

[0205] Benzotriazole: 1 part

[0206] Ammonium dihydrogen phosphate: 1 part

[0207] Dimethyl silicone oil, polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a silicon-containing composition 9 for processing chlorine-containing polyolefin materials.

[0208] Comparative Example 4

[0209] The polyethylene wax is used to replace the modified polysiloxane to prepare a composition for processing chlorine-containing polyolefin materials. The components of the composition are as follows:

[0210] Polyethylene wax: 60 parts

[0211] Erucic acid amide: 30 parts

[0212] Zinc stearate: 8 parts

[0213] Benzotriazole: 1 part

[0214] Ammonium dihydrogen phosphate: 1 part

[0215] Polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a composition 10 for processing chlorine-containing polyolefin materials.

[0216] Comparative Example 5

[0217] The modified polysiloxane is replaced by erucic acid amide to prepare a composition for processing chlorine-containing polyolefin materials, and the components of the composition are as follows:

[0218] Polyethylene wax: 30 parts

[0219] Erucic acid amide: 60 parts

[0220] Zinc stearate: 8 parts

[0221] Benzotriazole: 1 part

[0222] Ammonium dihydrogen phosphate: 1 part

[0223] Polyethylene wax, erucic acid amide, zinc stearate, benzotriazole and ammonium dihydrogen phosphate are added into a reaction kettle in proportion, melt-mixed evenly, and then droplet granulation is performed to obtain a composition 11 for processing chlorine-containing polyolefin materials.

[0224] Test example

[0225] The silicon-containing compositions 1-6 for processing chlorine-containing polyolefin materials prepared in Examples 1-6 and the compositions 6-11 for processing chlorine-containing polyolefin materials prepared in Comparative Examples 1-6 were used as test samples for testing.

[0226] Experiment on Processing Performance of Polyvinyl Chloride (PVC) Composite Materials

[0227] 1. Add the test sample to the PVC composite material, mix the components evenly in a high-speed mixer, use a torque rheometer to test the lubrication effect, and examine the residual material on the rotor at the same mixing time and the difficulty of cleaning the rotor for rating. The formula is shown in Table 1.

[0228] Table 1 Ratio of raw materials for PVC composite materials

[0229]

[0230] 2. The test results of PVC composite materials are shown in Table 2.

[0231] Note: The lubrication effect of the torque rheometer is measured at 180°C and 80 rpm. The residual material on the rotor is tested and rated after 5 minutes and 10 minutes respectively.

[0232] Table 2 PVC composite material processing extrusion performance test results

[0233]

[0234] The material residue level 1-5 represents the residue from less to more, and the rotor cleaning difficulty level 1-5 represents from easy to difficult.

[0235] In summary, the silicon-containing composition provided by the present invention can be applied to the PVC composite material to significantly improve the processing performance of the PVC composite material, and also improve the problem of the PVC material sticking to the screw after degradation.

[0236] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A silicon-containing composition for processing chlorinated polyolefin materials, characterized in that: The raw material components include 5 to 95 parts of modified polysiloxane, 5 to 95 parts of hydrocarbon wax, 5 to 95 parts of fatty amide, 5 to 95 parts of metal soap and 1 to 5 parts of other additives by weight.

2. The silicon-containing composition for processing chlorinated polyolefin materials according to claim 1, characterized in that: The raw material components include, by weight, 10 to 95 parts of modified polysiloxane, 10 to 95 parts of hydrocarbon wax, 10 to 95 parts of fatty amide, 10 to 95 parts of metal soap, and 1 to 5 parts of other additives.

3. The silicon-containing composition for processing chlorinated polyolefin materials according to claim 1, characterized in that: The hydrocarbon wax includes at least one of polyethylene wax, chlorinated polyethylene wax, oxidized polyethylene wax, oxidized chlorinated polyethylene wax, polypropylene wax, chlorinated polypropylene wax, oxidized polypropylene wax, oxidized chlorinated polypropylene wax, paraffin wax, Fischer-Tropsch wax, and montan wax.

4. The silicon-containing composition for processing chlorinated polyolefin materials according to claim 1, characterized in that: The fatty amide includes at least one of erucamide, oleamide, stearamide, ethylenebisstearamide, ethylenebisoleamide, and octadecylerucamide.

5. The silicon-containing composition for processing chlorinated polyolefin materials according to claim 1, characterized in that: The metal soap includes at least one of lead stearate, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, sodium stearate, lithium stearate, lead oleate, zinc oleate, calcium oleate, sodium oleate, and lead erucate.

6. The silicon-containing composition for processing chlorinated polyolefin materials according to any one of claims 1 to 5, characterized in that: The other auxiliary agent includes at least one of the features (1-1) to (1-4): (1-1) other auxiliary agents include at least one of antioxidants, antistatic agents, anti-ultraviolet agents, and antibacterial agents; the antioxidant includes at least one of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, N-phenyl-α-naphthylamine, alkyl phenothiazine, benzotriazole, mercaptobenzothiazole, 2,6-di-tert-butyl-p-cresol, N-cyclohexyl-N'-phenyl-p-phenylenediamine, triphenyl phosphite, diphenyl-isooctyl phosphite, and tributyl phosphite; (1-2) other additives include at least one of antioxidants, antistatic agents, anti-ultraviolet agents, and antibacterial agents; the anti-ultraviolet agent includes at least one of o-hydroxybenzoic acid phenyl ester, 2,2',4,4'-tetrahydroxybenzophenone, and 2-(2, hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; (1-3) other additives include at least one of antioxidants, antistatic agents, anti-ultraviolet agents, and antibacterial agents; the antibacterial agent includes at least one of silver ion antibacterial agent, zinc oxide, copper oxide, ammonium dihydrogen phosphate, lithium carbonate, sodium pentachlorophenol, p-nitrophenol, glutaraldehyde, and ethylene glycol methyl ether; (1-4) Other additives include at least one of antioxidants, antistatic agents, anti-ultraviolet agents, and antibacterial agents; the antistatic agent includes at least one of trimethylammonium stearate chloride, dimethylpentyl ammonium stearate chloride, alkyl tertiary amine sodium nitrate, trihydroxyethyl methyl quaternary ammonium sodium sulfate, N,N-hexadecylethyl morpholine sodium sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sodium polyacrylate, and sodium polystyrene sulfonate.

7. The silicon-containing composition for processing chlorinated polyolefin materials according to any one of claims 1 to 6, characterized in that: The structural formula of the modified polysiloxane is shown in general formula (1): R 7 , R 8 , R 18 , R 19 , R 20 , R 21 are each independently a monovalent organic group or atom; n is an integer greater than 1; R 7 , R 8 , R 18 , R 19 , R 20 , R 21 The structures are each independently selected from one of the general formulae (1-1) to (1-4): -C a H (2a+1) (1-1) -C b H (2b-1) (1-2) a is an integer greater than 0; b is an integer greater than 1; R 1 The structure is selected from the general formula (1-1) or (1-2); R 2 , R 3 , R 4 , R 5 The structures of are independently selected from the general formula (1-1) or (1-2); R 2 , R 3 , R 4 , R 5 In the structure, there is at least one A, A is as shown in the general formula (1-1) and a>8; R 10 , R 11 , R 12 , R 13 , R 14 The structures of are each independently selected from one of the general formulae (1-1) to (1-3) and (1-5): R 10 , R 11 , R 12 , R 13 There is at least one B, B is as shown in general formula (1-3); R 6 , R 9 , R 15 As shown in general formula (1-6), -C c H 2c - (1-6) c is an integer greater than 1; R 16 is one of a hydrogen atom, an alkyl group, a halogenated alkyl group, and an alkyl group containing a polar group; in the alkyl group, the halogenated alkyl group, and the alkyl group containing a polar group, the number of carbon atoms is an integer of 10 to 100; R 17 It is one of a hydrogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, an epoxyalkoxy group, a carboxylic acid alkoxy group, a hydroxyl group, and a halogen atom; in the alkyl group, the alkoxy group, the epoxyalkoxy group, and the carboxylic acid alkoxy group, the number of carbon atoms is an integer greater than 1.

8. The silicon-containing composition for processing chlorinated polyolefin materials according to claim 7, characterized in that: The preparation method of modified polysiloxane comprises the following steps: S1 alkyl-containing cyclosiloxane is subjected to ring-opening polymerization to obtain alkyl-containing single-terminal hydrogen-containing polysiloxane; S2 is a cyclosiloxane containing a polar functional group, and is subjected to ring-opening polymerization to obtain a single-terminal hydrogen-containing polysiloxane containing a polar functional group; S3: Mixing a single-terminal hydrogen-containing polysiloxane containing an alkyl group, a single-terminal hydrogen-containing polysiloxane containing a polar functional group, and a vinyl-containing polysiloxane, and subjecting the mixture to a catalytic reaction to obtain a modified polysiloxane.

9. The silicon-containing composition for processing chlorinated polyolefin materials according to claim 8, characterized in that: The reaction molar ratio of the alkyl-containing single-end hydrogen-containing polysiloxane, the polar functional group-containing single-end hydrogen-containing polysiloxane, and the vinyl-containing polysiloxane is 10-99:10-99:1-99.

10. A method for preparing a silicon-containing composition for processing chlorine-containing polyolefin materials according to any one of claims 1 to 9, characterized in that: The steps include: S1 modified polysiloxane, hydrocarbon wax, fatty amide, metal soap and other additives are blended at high temperature to obtain a mixed material; The S2 mixed material is granulated by droplet granulation to obtain a silicon-containing composition for processing chlorine-containing polyolefin materials.

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