Preparation method of phenyl trapezoidal polysilsesquioxane modified wear-resistant polyurethane

Abstract

The invention discloses a preparation method of phenyl trapezoid polysilsesquioxane modified wear-resistant polyurethane, which comprises the following steps: uniformly dispersing phenyl trapezoid polysilsesquioxane and epoxy propyl phenyl ether in a solvent, adding a catalyst, and reacting at 70-130 DEG C for 5-10 hours to obtain polyhydric alcohol with end carbon alcohol hydroxyl of the epoxy propyl phenyl ether. Uniformly dispersing the prepolymer, conventional polyol and excessive diisocyanate in a solvent, adding a catalyst, and reacting at 50-100 DEG C for 20 minutes to 2 hours, so as to obtain an isocyanate group-terminated prepolymer; and mixing the prepolymer with an arylamine chain extender, and carrying out a reaction in a mold at 80-120 DEG C for 2-10 h to obtain the phenyl trapezoidal polysilsesquioxane wear-resistant polyurethane workpiece. The polyurethane obtained by the invention can be used in high-wear environments, such as the inner wall of a grinding machine and the inner wall of a rolling mixer.

Description

Technical Field

[0001] The invention relates to the field of wear-resistant materials, in particular to a method for preparing a wear-resistant and high-hardness polyurethane system. Background Art

[0002] Wear is a common and inevitable phenomenon. The losses caused by wear in the national economy are quite alarming. Therefore, researching and developing new wear-resistant materials is a topic that is always worth exploring. Coating technology is a commonly used surface treatment technology, which has a significant effect on reducing friction losses. The resins used in wear-resistant coatings are mainly divided into three categories, namely epoxy resins, polyurethane resins, silicone resins and their respective modified products. Among all wear-resistant resins, epoxy wear-resistant resins are more common, and polyurethane has the best wear resistance, especially elastic polyurethane. Polyurethane has the characteristics of wear resistance, tear resistance, oil resistance, chemical corrosion resistance, good adhesion to other materials, high elasticity and strong vibration absorption ability, and polyurethane products have various forms, including soft, semi-rigid and rigid foam plastics, elastomers, paints and coatings, adhesives, sealants, synthetic leather coating resins, elastic fibers, etc., which are widely used in many fields such as automobile manufacturing, refrigerator manufacturing, transportation, civil engineering, footwear, synthetic leather, fabrics, petrochemicals, mining machinery, aviation, medical treatment, agriculture, etc. Although polyurethane materials have many advantages, with the progress of society and the development of industry, people have put forward higher requirements for polyurethane materials, especially the demand for new functional polyurethane elastomer materials with self-lubrication, self-repairing and high wear resistance.

[0003] Cross-linked networks have attracted the attention of researchers because they can provide stable polymer networks and meet the needs of different materials in pursuit of high mechanical properties. Inspired by the stable network structure of spider webs, we introduce an appropriate amount of chemical cross-linking to form polymers to achieve a special regular structure with a series of good physical properties.

[0004] Phenyl ladder polysilsesquioxane is an intramolecular organic-inorganic hybrid compound composed of an inorganic skeleton composed of two elements, silicon and oxygen, and an organic group surrounding it. It is similar in size to the chain segments and random coils of most other polymers. Introducing it into the polymer system can form a strong chemical reaction between the inorganic phase and the organic phase, making them well compatible, and can improve or even eliminate the problems of agglomeration of inorganic particles and weak bonding force between the two phases. Its core is a ladder-shaped structure composed of two silicon oxide chains in parallel, with phenyl groups located on the side of the ladder structure and the ladder end groups connected to hydroxyl groups. The length n of the ladder chain can be adjusted according to the needs of the application. The benzene ring and the ladder chain of silicon oxide give this structure excellent mechanical properties, high temperature stability, chemical durability and weather resistance; while the terminal hydroxyl groups give this material good solvent solubility, reactivity and film-forming properties.

[0005] The invention discloses a preparation method of phenyl ladder polysilsesquioxane modified wear-resistant polyurethane, wherein silanol and glycidyl phenyl ether are uniformly dispersed in a solvent to obtain a polyol with a carbon chain under a catalyst, and then the polyol and an excess of diisocyanate are uniformly dispersed in a solvent, and then a catalyst is added to pre-react to obtain a prepolymer linear structure polyurethane; the polyurethane prepolymer is further reacted with a chain extender to finally obtain a chain extender; the obtained chain extender is cured and cross-linked with the polyol, the solvent is extracted by a vacuum water pump, and the polyol is quickly poured into a preheated mold after degassing, and then put into a blast oven for curing, demoulding, and obtaining a cured product. Summary of the invention

[0006] The invention discloses a method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane, which utilizes an acetylacetone metal catalyst to achieve the transformation of silanol to carbon alcohol and the increase of molecular weight, and utilizes the rigid and flexible structure of phenyl ladder polysilsesquioxane to improve the wear resistance of polyurethane, so that the polyurethane has better structural stability, wear resistance and high hardness after thermal curing.

[0007] In order to achieve the above objectives, the following technical solutions are provided:

[0008] The invention discloses a method for preparing a wear-resistant polyurethane modified with phenyl ladder polysilsesquioxane:

[0009] (1) dissolving phenyl ladder polysilsesquioxane containing silanol hydroxyl groups and glycidyl phenyl ether in a first solvent, adding a first catalyst, reacting at 70-130° C. for 5-10 hours, and drying to obtain a polyol containing terminal carbon alcohol hydroxyl groups of polyglycidyl phenyl ether.

[0010] (2) 0.05-0.2 moles of a polyol containing carbonyl groups obtained in the reaction (1), 1 mole of a polyol for conventional polyurethane, and 2.1-2.4 moles of a diisocyanate are mixed in a second solvent, and then a second catalyst is added and the temperature is raised to 50-100° C. for reaction for 20 minutes to 2 hours to obtain an isocyanate-terminated prepolymer.

[0011] (3) The prepolymer obtained by the reaction in (2) is mixed with an aromatic amine chain extender, pressed into a mold, and reacted at 80-120 degrees for 2-10 hours to finally obtain a polyurethane workpiece enhanced with wear resistance by phenyl ladder polysilsesquioxane.

[0012] Preferably, the first solvent is dimethyl sulfoxide, N-methylpyrrolidone, etc., but not limited thereto.

[0013] Preferably, the second solvent is N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, toluene, chloroform, or dichloromethane.

[0014] Preferably, the first catalyst is aluminum acetylacetonate, cobalt acetylacetonate, triethylborane, etc., but is not limited thereto.

[0015] Preferably, the second catalyst is dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dicedecanoate, but is not limited thereto.

[0016] Preferably, the diisocyanate is diphenylmethane diisocyanate or toluene diisocyanate, but is not limited thereto.

[0017] Preferably, the polyol used in the conventional polyurethane is polytetramethylene glycol, polypropylene oxide glycol, polyether glycol, but is not limited thereto.

[0018] Preferably, the aromatic amine chain extender is diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminophenylmethane, or p-phenylenediamine, but is not limited thereto.

[0019] The beneficial effect of the present invention is that the excellent properties of phenyl ladder polysilsesquioxane such as high strength, wear resistance, high hardness and corrosion resistance are combined with diisocyanate, and then reacted with prepolymer and chain extender diamine to form polyurethane. Compared with traditional polyurethane products, after curing, it has a cross-linked network structure with better structural stability, wear resistance and rigidity. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the structural diagram of (1) polyol in Example 1

[0021] Figure 2 This is the H NMR spectrum of (1) polyol in Example 1 Specific implementation methods

[0023] In order to make the purpose, technical scheme and advantages of the present invention more clear, the present invention is further described in detail in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0024] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0025] Example 1

[0026] (1) Phenyl ladder polysilsesquioxane containing silanol hydroxyl groups and glycidyl phenyl ether are dissolved in xylene, aluminum acetylacetonate is added, reacted at 70° C. for 10 hours, and dried to obtain a polyol containing carboxyl hydroxyl groups.

[0027] (2) 0.05 mole of the polyol containing carbonyl hydroxyl groups obtained in the reaction (1), 1 mole of polytetramethylene polyol, and 2.1 moles of toluene diisocyanate are mixed in toluene, and then dibutyltin dilaurate is added and the temperature is raised to 50° C. for reaction for 2 hours to obtain a prepolymer with isocyanate end groups.

[0028] (3) The prepolymer obtained in the reaction of (2) is mixed with diethyltoluenediamine, pressed into a mold, and reacted at 80 degrees for 10 hours to finally obtain a polyurethane workpiece with enhanced wear resistance of phenyl ladder polysilsesquioxane.

[0029] Example 2

[0030] (1) Phenyl ladder polysilsesquioxane containing silanol hydroxyl groups and glycidyl phenyl ether are dissolved in xylene, aluminum acetylacetonate is added, reacted at 130° C. for 5 hours, and dried to obtain a polyol containing carboxyl hydroxyl groups.

[0031] (2) 0.2 moles of the polyol containing carbonyl groups obtained in the reaction (1), 1 mole of polytetramethylene glycol, and 2.4 moles of toluene diisocyanate are mixed in toluene, and then dibutyltin dilaurate is added and the temperature is raised to 100° C. for reaction for 20 minutes to obtain a prepolymer with isocyanate end groups.

[0032] (3) The prepolymer obtained in the reaction of (2) is mixed with diethyltoluenediamine, pressed into a mold, and reacted at 120 degrees for 2 hours to finally obtain a polyurethane workpiece with phenyl ladder polysilsesquioxane enhanced wear resistance.

[0033] Example 3

[0034] (1) Phenyl ladder polysilsesquioxane containing silanol hydroxyl groups and glycidyl phenyl ether are dissolved in toluene, cobalt acetylacetonate is added and reacted at 100° C. for 8 hours, and then dried to obtain a polyol containing carboxyl hydroxyl groups.

[0035] (2) 0.01 mole of the polyol containing carbonyl hydroxyl groups obtained in the reaction (1), 1 mole of polytetramethylene polyol, and 2.2 moles of diphenylmethane diisocyanate are mixed in toluene, and then dioctyltin dilaurate is added and the temperature is raised to 90° C. for reaction for 1 hour to obtain a prepolymer with isocyanate terminal groups.

[0036] (3) The prepolymer obtained by the reaction of (2) is mixed with 3,3'-dichloro-4,4'-diaminophenylmethane, pressed into a mold, and reacted at 100 degrees for 8 hours to finally obtain a polyurethane workpiece with phenyl ladder polysilsesquioxane enhanced wear resistance.

[0037] Example 4

[0038] (1) Phenyl ladder polysilsesquioxane containing silanol hydroxyl groups and glycidyl phenyl ether are dissolved in toluene, aluminum acetylacetonate is added, reacted at 110° C. for 8 hours, and dried to obtain a polyol containing carboxyl hydroxyl groups.

[0039] (2) 0.1 mole of a polyol containing carbonyl groups obtained in reaction (1), 1 mole of polypropylene oxide polyol, and 2.2 moles of diphenylmethane diisocyanate are mixed in xylene, and then dibutyltin dilaurate is added and the temperature is raised to 100°C for reaction for 30 minutes to obtain a prepolymer with isocyanate end groups.

[0040] (3) The prepolymer obtained by the reaction of (2) is mixed with 3,3'-dichloro-4,4'-diaminophenylmethane, pressed into a mold, and reacted at 100 degrees for 8 hours to finally obtain a polyurethane workpiece with phenyl ladder polysilsesquioxane enhanced wear resistance.

[0041] Example 5

[0042] (1) Phenyl ladder polysilsesquioxane containing silanol hydroxyl groups and glycidyl phenyl ether are dissolved in xylene, aluminum acetylacetonate is added and reacted at 100° C. for 8 hours, and then dried to obtain a polyol containing carboxyl hydroxyl groups.

[0043] (2) 0.2 moles of a polyol containing carbonyl groups obtained in reaction (1), 1 mole of polypropylene oxide polyol, and 2.4 moles of toluene diisocyanate are mixed in dioxane, and then dibutyltin dilaurate is added and the temperature is raised to 100°C for reaction for 20 minutes to obtain an isocyanate-terminated prepolymer.

[0044] (3) The prepolymer obtained by the reaction of (2) is mixed with 3,3'-dichloro-4,4'-diaminophenylmethane, pressed into a mold, and reacted at 120 degrees for 10 hours to finally obtain a polyurethane workpiece with phenyl ladder polysilsesquioxane enhanced wear resistance.

[0045] Example 6

[0046] (1) Phenyl ladder polysilsesquioxane containing silanol hydroxyl groups and glycidyl phenyl ether are dissolved in dimethyl sulfoxide, cobalt acetylacetonate is added and reacted at 90° C. for 8 hours, and then dried to obtain a polyol containing carboxyl hydroxyl groups.

[0047] (2) 0.2 moles of the polyol containing carbonyl groups obtained in the reaction (1), 1 mole of polypropylene oxide polyol, and 2.4 moles of toluene diisocyanate are mixed in N,N-dimethylformamide, and then dibutyltin dilaurate is added and the temperature is raised to 95°C for reaction for 2 hours to obtain a prepolymer with isocyanate end groups.

[0048] (3) The prepolymer obtained by the reaction of (2) is combined with diethyltoluenediamine, pressed into a mold, and reacted at 100 degrees for 10 hours to finally obtain a polyurethane workpiece with phenyl ladder polysilsesquioxane enhanced wear resistance.

[0049] Table 1: Hardness and wear resistance test table of a wear-resistant and high-hardness thermosetting polyurethane

[0050] Example Shore A hardness <![CDATA[Akron Wear / mm 3 > Example 1 98 10 Example 2 91 17 Example 3 96 12 Example 4 93 15 Example 5 97 11 Example 6 94 14

Claims

1. A method for preparing a wear-resistant polyurethane modified with phenyl ladder polysilsesquioxane, characterized in that: (1) dissolving a phenyl ladder polysilsesquioxane containing a silanol hydroxyl group and glycidyl phenyl ether in a first solvent, adding a first catalyst and reacting at 70-130° C. for 5-10 hours, and drying to obtain a polyol containing a terminal carbon alcohol hydroxyl group of polyglycidyl phenyl ether; (2) mixing 0.05-0.2 moles of the polyol containing carbonyl groups obtained in the reaction of (1), 1 mole of a polyol for conventional polyurethane, and 2.1-2.4 moles of a diisocyanate in a second solvent, adding a second catalyst, heating to 50-100° C., and reacting for 20 minutes to 2 hours to obtain a prepolymer having an isocyanate terminal group; (3) The prepolymer obtained by the reaction in (2) is mixed with an aromatic amine chain extender, pressed into a mold, and reacted at 80-120 degrees for 2-10 hours to finally obtain a polyurethane workpiece enhanced with wear resistance by phenyl ladder polysilsesquioxane.

2. The method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane according to claim 1, characterized in that: The first solvent is dimethyl sulfoxide, N-methylpyrrolidone, etc., but is not limited thereto.

3. The method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane according to claim 1, characterized in that: The second solvent is N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, toluene, chloroform, dichloromethane, but is not limited thereto.

4. The method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane according to claim 1, characterized in that: The first catalyst is aluminum acetylacetonate, cobalt acetylacetonate, triethylborane, etc., but is not limited thereto.

5. The method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane according to claim 1, characterized in that: The second catalyst is dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dicedecanoate, but is not limited thereto.

6. The method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane according to claim 1, characterized in that: The diisocyanate is diphenylmethane diisocyanate or toluene diisocyanate, but is not limited thereto.

7. The method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane according to claim 1, characterized in that: The polyols used in the conventional polyurethane are polytetramethylene glycol, polypropylene oxide glycol, polyether glycol, but are not limited thereto.

8. The method for preparing a wear-resistant polyurethane modified by phenyl ladder polysilsesquioxane according to claim 1, characterized in that: The aromatic amine chain extender is diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminophenylmethane, and p-phenylenediamine, but is not limited thereto.

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