Preparation method of hydroxyl polyurethane high polymer material

Abstract

The invention discloses a preparation method of a hydroxyl polyurethane high polymer material, and relates to the technical field of high polymer chemistry, the preparation method comprises the following steps: firstly, carrying out melt blending on a certain thermoplastic elastomer and a thermoplastic elastomer TPV to obtain a material preparation substrate; then taking the substrate and the prepared octagonal polyhedral oligomeric silsesquioxane POSS as a cross-linking agent to obtain an intermediate product, namely the octagonal polyhedral oligomeric silsesquioxane POSS containing the hydroxyl polyurethane nano composite material; catalyzing the intermediate product through an organic metal tin catalyst to obtain a master batch; adding an acetylated hindered amine light stabilizer HALS into the intermediate product as a light stabilizer auxiliary material to obtain a mixed master batch; other processing aids, namely a lubricant and a coloring agent, are added; and then carrying out dynamic vulcanization, bracing, cooling and grain-sized dicing by using a double-screw extruder to obtain the final hydroxyl polyurethane high polymer material. The material is advanced in preparation process, has the characteristics of good extensibility, storage stability, low cost and excellent transportation, has reducibility, and is green and environment-friendly.

Description

Technical Field

[0001] The present invention relates to polymer chemistry technology, and specifically relates to a preparation method of a hydroxyl polyurethane polymer material. Background Art

[0002] As a polymer material, the hydroxyl polyurethane in the present invention, in the masterbatch obtained after being catalyzed by organotin metal, contains basic chemical groups in its chemical structure, namely hydroxyl groups and amino groups, which provide superior conditions for the stiffness, hardness and flexibility of the material itself; these functional groups that have undergone thermal polymerization rearrangement reactions enable it to maintain the stability of the material when subjected to external forces, that is, the important parameters obtained during the observation of the material, including corrosion resistance, flexural fatigue resistance, cold resistance, impact resistance, impact force resistance, stress resistance and other related important parameters, have been significantly improved compared with other polyurethane material processing technologies; at the same time, after the styrene block copolymer SEBS reacts with the organic hybrid octahedral polyhedral oligomeric silsesquioxane POSS, a high-performance crosslinking agent, the glass transition temperature of the material is increased; meanwhile, innovatively, under the homogeneous catalysis of a solvent by an organotin catalyst, a poly(ethylene terephthalate) PET and polypropylene PP composite system is used to carry out a hydrosilylation addition reaction, generating a σ-rearrangement reaction, and a crosslinking synthesis method of a polymer compound with a relatively rich topological structure is obtained, so that the material presents a simple and non-redundant topological structure under the observation of a transmission electron microscope. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation method of a hydroxyl polyurethane polymer material to solve the above deficiencies in the prior art.

[0004] To achieve the above purpose, the present invention provides the following technical solution: A preparation method of a hydroxyl polyurethane polymer material, comprising the following steps:

[0005] S1. Melting and blending a thermoplastic elastomer with a TPV thermoplastic elastomer to obtain a polymer material substrate;

[0006] S2. Crosslinking the styrene block copolymer SEBS with the organic hybrid octahedral polyhedral oligomeric silsesquioxane POSS as a crosslinking agent to obtain an intermediate product containing a hydroxyl polyurethane nanocomposite octahedral polyhedral oligomeric silsesquioxane POSS;

[0007] S3. Subjecting the polymer material substrate prepared in S1 and the hydroxyl polyurethane nanocomposite octahedral polyhedral oligomeric silsesquioxane POSS prepared in S2 to homogeneous catalysis in a solvent with the participation of an organotin catalyst, and then carrying out a hydrosilylation addition reaction and generating a σ-rearrangement reaction under the action of a composite system to obtain a masterbatch;

[0008] S4. Add a light stabilizer material to the intermediate product obtained in S3 to prepare a masterbatch.

[0009] S5. Add the masterbatch prepared in S4 to a twin-screw extruder, and add a lubricant and a colorant to prepare a masterbatch.

[0010] S6. After dynamically vulcanizing, strand extruding, cooling, and pelletizing the masterbatch described in S5, the final hydroxyl polyurethane polymer material is obtained.

[0011] Further, the thermoplastic elastomer in S1 is a saturated hydrogenated TPE thermoplastic elastomer SEBS.

[0012] Further, the crosslinking process in S2 can retain the nanostructure of the organic hybrid octahedral silsesquioxane POSS and uniformly disperse it in the styrene block copolymer SEBS matrix.

[0013] Further, the catalyst in S3 is an organotin.

[0014] Further, the composite system in S3 is a composite system of polyethylene terephthalate PET and polypropylene PP.

[0015] Further, the light stabilizer material in S4 is an acetylated hindered amine light stabilizer HALS prepared by formulation.

[0016] Further, the lubricant and the colorant in S5 are added at the feeding zone position of the twin-screw extruder.

[0017] Further, the lubricant in S5 is zinc stearate or calcium stearate.

[0018] Further, the colorant in S5 is one of titanium dioxide, metal oxides, carbon black, or metal sulfides.

[0019] Further, the screw speed of the twin-screw extruder in S6 is 300 - 500 rpm / min, the screw length-diameter ratio is 36 - 64, the processing temperature is 140 - 220 °C, and the rotational speed of the rotor in the screw mixing zone is 15 - 30 m / s. -1 。

[0020] Compared with the prior art, a method for preparing a hydroxyl polyurethane polymer material provided by the present invention has the characteristics of extensibility, storage stability, low cost, excellent conveyance, corrosion resistance, low temperature resistance, high temperature resistance, and aging resistance. The material has good environmental protection performance, does not contain benzene, tar, and other polluting solvents, has good green environmental protection and pollution-free performance, the preparation process is advanced, the raw materials used in the preparation are easy to produce, the equipment performance is leading, and the overall processing and preparation process has been optimized and leapfrogged.

[0021] This hydroxyl polyurethane polymer material can be produced, processed and promoted globally, and is applied in the field of advanced machining and manufacturing, including infrastructure construction such as the automotive industry, building materials, aerospace industry, and bridge sections. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required in the embodiments. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings.

[0023] Figure 1 Schematic diagram of the preparation process provided by the embodiment of the present invention;

[0024] Figure 2 Schematic diagram of the twin-screw extruder provided by the embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0025] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the following will further introduce the present invention in detail with reference to the drawings.

[0026] Embodiment 1:

[0027] Please refer to Figure 1 - Figure 2 , a method for preparing a hydroxyl polyurethane polymer material, comprising the following steps:

[0028] S1. Melting and blending the saturated hydrogenated TPE thermoplastic elastomer SEBS and the TPV thermoplastic elastomer to obtain a polymer material substrate;

[0029] The saturated hydrogenated TPE thermoplastic elastomer SEBS and the TPV thermoplastic elastomer have good compatibility, and the saturated hydrogenated TPE thermoplastic elastomer SEBS can improve the mechanical properties, low-temperature properties, heat resistance, chemical corrosion resistance and oil resistance of the product.

[0030] SEBS is a new type of modified thermoplastic elastomer prepared by selectively hydrogenating the unsaturated double bonds in the polybutadiene segment of the styrene-butadiene-styrene block copolymer (SBS). It has the characteristics of excellent weather resistance, good physical properties, multi-phase structure and wide application fields.

[0031] TPV is short for thermoplastic vulcanized rubber, which combines the elasticity of rubber and the processability of thermoplastic plastics.

[0032] S2. Crosslink the styrene block copolymer SEBS with the organic hybrid octahedral polyhedral oligomeric silsesquioxane POSS to obtain the octahedral polyhedral oligomeric silsesquioxane POSS containing a hydroxyl polyurethane nanocomposite;

[0033] The organic hybrid octahedral polyhedral oligomeric silsesquioxane POSS can simultaneously be used as an adjuvant and a crosslinking agent during the glass transition process, raising the glass transition temperature and improving the luminescence of quantum dots under an optical microscope. The glass transition temperature (Tg) refers to the transition of polymer segments from a high elastic state to a glassy state. The glass transition temperature (Tg) is an important physical property of amorphous polymers and also an important issue and difficult problem in the basic theory of condensed matter physics. It involves many frontier issues related to kinetics and thermodynamics. Combining the FEA nonlinear data analysis method: Solve a problem of elastic and fatigue properties, the material viscoplasticity theory and the stress equation;

[0034] S3. Subject the polymer material substrate prepared in S1 and the octahedral polyhedral oligomeric silsesquioxane POSS containing a hydroxyl polyurethane nanocomposite prepared in S2 to solvent homogeneous catalysis with an organotin catalyst, and then carry out a hydrosilylation addition reaction and a σ-rearrangement reaction under the action of a composite system of polyethylene terephthalate PET and polypropylene PP to obtain an intermediate product;

[0035] During the further processing and synthesis of the organic hybrid octahedral polyhedral oligomeric silsesquioxane POSS with an organotin catalyst, the physical and chemical properties and mechanical properties of the material in the overall processing project can be improved, including corrosion resistance, flexural fatigue resistance, cold resistance, impact resistance, impact force resistance, stress resistance, volume crystallinity, Shore hardness, dsc melting point, glass transition temperature and ultimate tensile strength.

[0036] In this step, using the method of computational chemistry, it is found through observation under a scanning electron microscope that the C-C bond that best matches the mechanical force stretching direction of the prepared material and the composite system is highly selectively activated.

[0037] S4. Add a prepared acetylated hindered amine light stabilizer material to the intermediate product prepared in S3 to prepare a masterbatch;

[0038] By adding a prepared acetylated hindered amine light stabilizer HALS material as the light stabilizer material, the hydroxyl polyurethane polymer material is enabled to have the ability to capture the active free radicals generated in the polymer, showing excellent photocatalytic activity in the ultraviolet light and visible light ranges, so that the overall material has a wide light absorption range, that is, inhibiting the photooxidation process to achieve the purpose of light stabilization.

[0039] S5. Add the masterbatch prepared in S4 to the position in the 3-8 zones of the twin-screw extruder, and add lubricant and colorant to prepare a mixed masterbatch; the lubricant is zinc stearate; the colorant is titanium dioxide, metal oxide, carbon black or metal sulfide.

[0040] By adding lubricant, the fluidity of the material is improved and the friction is reduced; by adding colorant, the material is given a specific color. These components undergo strong shearing and mixing in the twin-screw extruder to form a uniform mixed masterbatch.

[0041] Zinc stearate is used as a lubricant in the fields of industrial rubber, industrial resin, etc.

[0042] Titanium dioxide is an inorganic compound and can be used as an additive in industrial resin.

[0043] S6. After the S5 mixed masterbatch is dynamically vulcanized, strip-drawn, cooled and pelletized by the twin-screw extruder, a hydroxyl polyurethane polymer material is obtained. The screw speed of the twin-screw extruder is 300 - 500 rpm / min, the screw length-diameter ratio is 36 - 64, and the processing temperature is 140 - 220 °C.

[0044] In the twin-screw extruder, the mixed masterbatch undergoes dynamic vulcanization under the action of high temperature and shear force. Dynamic vulcanization is a technique that simultaneously conducts cross-linking reaction during the extrusion process, which can significantly improve the physical properties and heat resistance of the material; after dynamic vulcanization, the molten material is shaped into strips by the die at the outlet of the extruder, and this step helps to initially determine the shape and size of the product; the pulled hot material strip quickly passes through the cooling device to reduce the temperature and solidify it, maintaining the required shape and size; finally, the cooled material strip is fed into the pelletizer and cut into particles of a certain length. These particles are the final product - the finished hydroxyl polyurethane polymer material.

[0045] The screw speed is 300 - 500 rpm / min. The choice of screw speed will affect the mixing effect and extrusion speed of the material. A higher speed can provide stronger shear force and better mixing effect, but it may also cause overheating of the material or unstable extrusion.

[0046] The screw length-diameter ratio is 36 - 64, which determines the residence time and mixing effect of the material in the extruder. A longer length-diameter ratio means that the material has a longer path and more sufficient mixing time in the extruder.

[0047] The processing temperature is 140 - 220 °C. The processing temperature is a key parameter to ensure the melting, mixing and vulcanization of the material. The choice of temperature needs to consider the melting point, thermal stability of the material and the requirements of cross-linking reaction.

[0048] Example 2:

[0049] Please refer to Figure 1 - Figure 2 , this embodiment provides a technical solution based on Embodiment 1: Replace the lubricant in S5 with calcium stearate instead of zinc stearate.

[0050] Calcium stearate is a white solid, insoluble in water but soluble in some organic solvents. When heated, it softens and melts into a fluid at higher temperatures. These physical properties make calcium stearate have unique advantages in a variety of industrial applications. Calcium stearate is stable at room temperature but is easily decomposed in a strong acid environment. Therefore, contact with strong acids should be avoided during storage and use.

[0051] Due to its various excellent properties, calcium stearate is widely used in various fields. As a heat stabilizer and lubricant in the plastic industry, calcium stearate can improve the processing performance and anti-aging performance of plastic products. In the processing of plastics such as polyvinyl chloride (PVC), calcium stearate can significantly improve the plasticity and molding efficiency of materials; in rubber processing, calcium stearate can be used as a vulcanizing agent and plasticizer to improve the elasticity and durability of rubber products. At the same time, it can also improve the processing performance of rubber, making rubber easier to mold and process.

[0052] Embodiment 3:

[0053] This embodiment provides a technical solution based on Embodiment 1: The rotational speed of the rotor in the screw mixing zone is 15 - 30 m / s -1 .

[0054] The rotor in the screw mixing zone provides a shearing action, and the shearing action has an important impact on the mixing effect of the material and the product quality. Appropriate shearing action helps the dispersion, mixing and plasticization of the material, but too strong shearing action may also cause the material to degrade or damage its structure.

[0055] In the description of the present invention, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features. The meaning of "a plurality" is two or more unless otherwise specifically defined.

[0056] In the present invention, unless otherwise clearly defined and limited, the terms such as "installed", "connected", "connected", "fixed", etc. should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or integrated; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication of two components or the interaction relationship between two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0057] In the present invention, unless otherwise clearly defined and limited, the first feature being "on" or "under" the second feature may be that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, the first feature being "above", "over" and "on top of" the second feature may be that the first feature is directly above or obliquely above the second feature, or merely means that the horizontal height of the first feature is higher than that of the second feature. The first feature being "under", "below" and "beneath" the second feature may be that the first feature is directly below or obliquely below the second feature, or merely means that the horizontal height of the first feature is less than that of the second feature.

[0058] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example" or "some examples", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In the drawings of the disclosed embodiments of the present invention, only the structures related to the disclosed embodiments are involved, and other structures may refer to the general design. Without conflict, the same embodiment and different embodiments of the present invention may be combined with each other.

[0059] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

[0060] Only some exemplary embodiments of the present invention have been described above by way of illustration. Without doubt, those of ordinary skill in the art can modify the described embodiments in various different ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and description are illustrative in nature and should not be construed as limiting the protection scope of the claims of the present invention.

Claims

1. A method for preparing a hydroxyl polyurethane polymer material, characterized in that, It includes the following steps: S1. Melt-blend a thermoplastic elastomer with a TPV thermoplastic elastomer to obtain a polymer material substrate; S2. Crosslink a styrene block copolymer SEBS with an organic hybrid octahedral silsesquioxane POSS to obtain an intermediate product - a hydroxyl polyurethane nanocomposite octahedral silsesquioxane POSS; S3. Use the polymer material substrate prepared in S1 and the intermediate product containing the hydroxyl polyurethane nanocomposite octahedral silsesquioxane POSS prepared in S2 as a crosslinking agent. At this time, the prepared product uses POSS as a capping group, and then through the participation of an organotin as a catalyst for solvent homogeneous catalysis to solve a problem of soft and hard segment and glass transition temperature; at the same time, use a composite system of polyethylene terephthalate PET and polypropylene PP. Under the action of this composite system, a hydrosilylation addition reaction and a σ-rearrangement reaction occur. After the reaction is completed, a masterbatch is obtained; S4. Add a prepared acetylated hindered amine light stabilizer material to the intermediate product prepared in S3 to obtain a mixed masterbatch; S5. Add the masterbatch prepared in S4 to a twin-screw extruder, and add a lubricant and a colorant; S6. After the mixed masterbatch described in S5 is dynamically vulcanized, drawn, cooled and pelletized by a twin-screw extruder, the final hydroxyl polyurethane polymer material is obtained.

2. The preparation method of a hydroxyl polyurethane polymer material according to claim 1, characterized in that, The thermoplastic elastomer described in S1 is a saturated hydrogenated TPE thermoplastic elastomer SEBS.

3. The preparation method of a hydroxyl polyurethane polymer material according to claim 1, characterized in that, The crosslinking process described in S2 can retain the nanostructure of the organic hybrid octahedral silsesquioxane POSS and uniformly disperse it in the styrene block copolymer SEBS matrix.

4. The preparation method of a hydroxyl polyurethane polymer material according to claim 1, characterized in that, The catalyst described in S3 is an organotin.

5. The preparation method of a hydroxyl polyurethane polymer material according to claim 1, characterized in that The composite system described in S3 is a composite system of polyethylene terephthalate PET and polypropylene PP.

6. The preparation method of a hydroxyl polyurethane polymer material according to claim 1, characterized in that, The light stabilizer material described in S4 is a prepared acetylated hindered amine light stabilizer HALS.

7. A method for preparing a hydroxyl polyurethane polymer material according to claim 1, characterized in that, The lubricant and the colorant described in S5 are added at the feeding zone position of the twin-screw extruder.

8. A method for preparing a hydroxyl polyurethane polymer material according to claim 1, characterized in that, The lubricant described in S5 is zinc stearate or calcium stearate; the colorant described in S5 is titanium dioxide, metal oxide, carbon black or metal sulfide.

9. A method for preparing a hydroxyl polyurethane polymer material according to claim 1, characterized in that, The screw speed of the twin-screw extruder described in S6 is 300 - 500 rpm / min, the screw length-diameter ratio is 36 - 64, and the processing temperature is 140 - 220 °C.

10. The preparation method of a hydroxyl polyurethane polymer material according to claim 1, wherein, The rotational speed of the rotor in the screw mixing zone of the twin-screw extruder described in S6 is 15 - 30 m.s -1 .

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