A kind of silicone modified polyurethane with wear-resistant effect and its preparation method and application

Abstract

The present invention provides a silicone-modified polyurethane with wear-resistant effect and a preparation method and application thereof, wherein the silicone-modified polyurethane is obtained by reacting a system comprising the following components: (a) a polyisocyanate having at least two isocyanate groups; (b) a polymer polyol mixture, which includes a polylactic acid polyol and a hydroxyl-containing silicone prepolymer; (c) a chain extender; (d) a capping agent having a long carbon chain hydrocarbon group, which has at least one isocyanate group reactive group. The present invention obtains a silicone-modified polyurethane having wear resistance, toughness enhancement, mechanical properties and hand feel by introducing crystalline polylactic acid segments, silicone segments and long carbon chain hydrocarbon groups into polyurethane. The silicone-modified polyurethane has good compatibility with most plastics, and adding the silicone-modified polyurethane to plastics can significantly improve the wear resistance, toughness, hydrophobicity and hand feel of the plastics.

Description

Technical Field

[0001] The invention belongs to the technical field of plastic additive additives, and specifically relates to an organosilicon-modified polyurethane with wear-resistant effect and a preparation method and application thereof. Background Art

[0002] Wear-resistant agent is a plastic additive that can improve the wear resistance of the material surface, prevent scratches on the material surface, and reduce friction between materials. Currently, the commonly used wear-resistant additives are molybdenum disulfide, graphite, glass fiber, carbon fiber, polytetrafluoroethylene, silicone oil, etc. Among them, molybdenum disulfide is mainly used to increase the crystallinity of nylon materials, and is mainly used for nylon plastics, and its application range is limited; graphite has a unique network structure that allows it to slide against each other with very small friction, but this wear-resistant property is particularly important in a water environment; glass fiber improves the wear resistance of thermoplastics by reinforcement, polytetrafluoroethylene and silicone oil can reduce the friction coefficient of plastics and thus improve the wear resistance of plastics, but the above-mentioned inorganic wear-resistant agents such as molybdenum disulfide, graphite, and glass fiber will mostly affect the toughness and feel of plastics, while polytetrafluoroethylene and silicone oil will affect the strength and mechanical properties of plastics.

[0003] Therefore, developing a wear-resistant material that has wear resistance and does not affect the toughness and mechanical strength of plastics is a technical problem that needs to be solved urgently in this field. Summary of the invention

[0004] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a silicone-modified polyurethane with wear resistance, a preparation method and an application thereof. By introducing crystalline polylactic acid segments, silicone segments and long carbon chain hydrocarbon groups into polyurethane, a silicone-modified polyurethane with wear resistance, toughness enhancement, mechanical properties and hand feel is obtained. The silicone-modified polyurethane has good compatibility with most plastics, and adding the silicone-modified polyurethane to plastics can significantly improve the wear resistance, toughness, hydrophobicity and hand feel of the plastics.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides an organosilicon-modified polyurethane, wherein the organosilicon-modified polyurethane is obtained by reacting a reaction system comprising the following components:

[0007] (a) a polyisocyanate having at least two isocyanate groups;

[0008] (b) a polymer polyol mixture comprising polylactic acid polyol and a hydroxyl-containing organosilicon prepolymer;

[0009] (c) chain extenders;

[0010] (d) A blocking agent having a long carbon chain hydrocarbon group, which has at least one isocyanate group-reactive group.

[0011] Preferably, the molar ratio between the isocyanate groups and the hydroxyl groups in the reaction system is 1.02-1.2.

[0012] Preferably, the mass ratio of polylactic acid polyol to hydroxyl-containing organopolysiloxane prepolymer in component (b) is (5-7):(3-5); wherein 5-7 may be 5.5, 6, 6.5, etc.; and 3-5 may be 3.5, 4, 4.5, etc.

[0013] Exemplarily, the polyisocyanate includes one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate trimer, xylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like.

[0014] Preferably, based on 100 parts by weight of the total weight of the reaction system, the amount of the component (d) end-capping agent having a long carbon chain hydrocarbon group added is 1 to 15 parts by weight; for example, it can be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, etc.

[0015] Preferably, based on 100 parts by weight of the total weight of the reaction system, the added amount of the component (c) chain extender is 1 to 5 parts by weight.

[0016] Preferably, the component (d) end-capping agent having a long carbon chain hydrocarbon group is a long carbon chain monofunctional amine compound.

[0017] Preferably, the component (d) end-capping agent having a long carbon chain hydrocarbon group includes an aliphatic primary amine having a carbon number of 15 to 22; for example, the carbon number may be 16, 17, 18, 19, 20, 21, etc.

[0018] The above-mentioned capping agent having a long carbon chain hydrocarbon group may include one or more of pentadecylamine, hexadecylamine, heptadecanylamine, octadecylamine, nonadecanylamine, eicosylamine, heneicosylamine, dodecylamine and the like.

[0019] Preferably, the component (d) comprises a dihydroxy chain extender and / or a trihydroxy chain extender.

[0020] Preferably, the dihydroxy chain extender includes one or more of ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, glycerol, trimethylolpropane, diethylene glycol, triethylene glycol, and neopentyl glycol.

[0021] Preferably, the molecular weight of the polylactic acid polyol is 1000-2000 g / mol.

[0022] Preferably, the hydroxyl-containing organopolysiloxane prepolymer comprises a double-terminal monohydroxyl organosilicon prepolymer and / or a single-terminal dihydroxyl organosilicon prepolymer.

[0023] The hydroxyl-containing organopolysiloxane prepolymer can be prepared according to methods known in the art, or purchased from the market.

[0024] Preferably, the viscosity of the hydroxyl-containing organopolysiloxane prepolymer is 15 to 100 cps.

[0025] The second aspect is that the present invention provides a method for preparing the above-mentioned organosilicon-modified polyurethane, and the preparation method comprises the following steps:

[0026] S1. reacting component (a) a polyisocyanate having at least two isocyanate groups and component (b) a polymer polyol mixture to obtain a prepolymer;

[0027] S2. After the prepolymer and the component (c) chain extender undergo a chain extension reaction, the prepolymer reacts with the component (d) end-capping agent, and then cools and crystallizes to obtain the silicone-modified polyurethane.

[0028] Preferably, in step S1, the reaction temperature is 70-80°C; the reaction time is 3-5h;

[0029] Preferably, the step S1 further comprises a catalyst;

[0030] Preferably, in step S2, the reaction time is 1 to 3 hours.

[0031] Preferably, the catalyst includes an organic tin catalyst, an organic bismuth catalyst, and the like.

[0032] Preferably, based on 100 parts by weight of the total weight of the raw materials in step S1, the amount of the catalyst added is 0.01-2 parts by weight.

[0033] Preferably, a proper amount of organic solvent may be added for dilution according to the actual reaction conditions, and the organic solvent may include acetone, butanone, butyl acetate, ethyl acetate, toluene, xylene and the like.

[0034] In a third aspect, the present invention provides an application of the above-mentioned organosilicon-modified polyurethane in plastic products.

[0035] In a fourth aspect, the present invention provides an anti-wear agent, which includes the above-mentioned organosilicon-modified polyurethane or the organosilicon-modified polyurethane prepared according to the above-mentioned preparation method.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] The present invention uses polyisocyanate, polymer polyol mixture (including polylactic acid polyol and hydroxyl-containing organosilicon prepolymer), end-capping agent with long carbon chain hydrocarbon group and chain extender as main raw materials to prepare organosilicon-modified polyurethane with wear-resistant effect, wherein the organosilicon segment has a tendency to be enriched on the surface, and the lower polarity can reduce the friction coefficient, and the excellent crystallinity of polylactic acid polyol, plus the lubricity brought by the long carbon chain hydrocarbon group at the end of the segment, together give the resin excellent wear resistance. At the same time, the organosilicon-modified polyurethane with wear-resistant effect not only has amino acid ester polar groups, but also has long carbon chain hydrocarbon non-polar groups, has excellent compatibility with most polymer resins, and can be added to polymer resins to give the polymer resins excellent wear resistance, toughness and feel, and can be applied to most polymer resin products. DETAILED DESCRIPTION

[0038] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0039] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art. In addition, "parts" and "%" in this specification, unless otherwise specified, represent "parts by mass" and "mass %" respectively.

[0040] Example 1

[0041] A silicone-modified polyurethane, the preparation method of which comprises the following steps:

[0042] (1) In a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, 50 g of dehydrated polylactic acid polyol (Fengyuan Biotechnology, PLA1000), 50 g of double-terminal monohydroxyl silicone prepolymer (Silok 8812, Guangzhou) and 40 g of 4,4'-dicyclohexylmethane diisocyanate (HMDI) were added, 0.05 g of an organic bismuth catalyst was added, the temperature was raised to 80°C, and the reaction was kept warm for 3 hours to obtain a prepolymer;

[0043] (2) 0.9 g of ethylene glycol and 0.6 g of trimethylolpropane were added to the above prepolymer, and the reaction was continued for 2 h. Then, 12 g of octadecylamine was added for end-capping, and the reaction was terminated. The temperature was lowered and crystallized to obtain a white solid silicone-modified polyurethane.

[0044] Example 2

[0045] A silicone-modified polyurethane, the preparation method of which comprises the following steps:

[0046] (1) In a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, 60 g of dehydrated polylactic acid polyol (PLA2000), 40 g of double-terminal monohydroxyl silicone prepolymer (Silok 8812) and 35 g of isophorone diisocyanate (IPDI) were added, 0.1 g of an organic bismuth catalyst was added, the temperature was raised to 75° C., and the reaction was kept at this temperature for 3.5 hours to obtain a prepolymer;

[0047] (2) 2.3 g of butanediol and 1 g of trimethylolpropane were added to the above prepolymer, and the reaction was continued for 1.5 h. Then, 9 g of pentadecylamine was added for end-capping. The reaction was terminated, the temperature was lowered, and crystallization was performed to obtain a white solid silicone-modified polyurethane.

[0048] Example 3

[0049] A silicone-modified polyurethane, the preparation method of which comprises the following steps:

[0050] (1) In a reaction kettle equipped with a stirrer, a reflux condenser and a thermometer, 70 g of dehydrated polylactic acid polyol (PLA1000), 30 g of double-terminal monohydroxyl silicone prepolymer (Silok 8812) and 45 g of diphenylmethane-4,4'-diisocyanate (MDI) were added, 1 g of an organic bismuth catalyst was added, the temperature was raised to 80°C, and the reaction was kept at this temperature for 3 hours to obtain a prepolymer;

[0051] (2) 4 g of propylene glycol and 0.5 g of propylene glycol were added to the above prepolymer, and the reaction was continued for 2 h. Then, 7.5 g of nonadecanamine was added for end-capping. The reaction was terminated, and the temperature was lowered and crystallized to obtain a white solid silicone-modified polyurethane.

[0052] Example 4

[0053] The difference between this embodiment and embodiment 1 is that n-octadecylamine is replaced by n-undecylamine in an equal molar amount.

[0054] Example 5

[0055] The difference between this embodiment and embodiment 1 is that the R value (n NCO :n OH ) remained unchanged, the mass ratio of polylactic acid polyol (PLA1000) and double-terminal monohydroxy silicone prepolymer (Silok 8812) was changed from 50:50 to 10:90.

[0056] Example 6

[0057] The difference between this embodiment and embodiment 1 is that the R value (n NCO :nOH ) remained unchanged, the mass ratio of polylactic acid polyol (PLA1000) and double-terminal monohydroxy silicone prepolymer (Silok 8812) was changed from 50:50 to 90:10.

[0058] Comparative Example 1

[0059] A silicone-modified polyurethane, which differs from Example 1 in that: the R value (n NCO :n OH ) remains unchanged, polylactic acid polyol is not added, and other raw materials, parameters and steps are the same as those in Example 1.

[0060] Comparative Example 2

[0061] A silicone-modified polyurethane, which differs from Example 1 in that: the R value (n NCO :n OH ) remains unchanged, no double-terminal monohydroxyl silicone prepolymer is added, and other raw materials, amounts, parameters and steps are the same as those in Example 1.

[0062] Comparative Example 3

[0063] A silicone-modified polyurethane, which differs from Example 1 in that octadecylamine is replaced by an equal molar amount of butylamine, and other raw materials, amounts, parameters and steps are the same as those in Example 1.

[0064] Application Examples 1 to 6, Comparative Application Examples 1 to 3

[0065] A wear-resistant TPU comprises 5 g of a wear-resistant agent, 100 g of a polyester TPU and 0.5 g of an antioxidant 1010.

[0066] The above-mentioned anti-wear agent is the organosilicon-modified polyurethane obtained in Examples 1 to 6 and Comparative Examples 1 to 3.

[0067] Performance Test:

[0068] The organosilicon-modified polyurethanes obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were crushed to obtain organosilicon-modified polyurethane powders. 5 g of the organosilicon-modified polyurethane powders, 100 g of polyester TPU and 0.5 g of antioxidant 1010 were mixed, and then extruded, cooled and granulated using a twin-screw extruder to obtain a plastic product. The plastic product was sampled and tested according to the following standards, and compared with a blank without addition. The test performance is shown in Table 1.

[0069] (1) Wear resistance test: The test was conducted in accordance with ASTM D5963; the wear resistance was expressed as a volume loss index in cubic millimeters. The smaller the volume loss value, the better the wear resistance, while the smaller the wear resistance index value, the worse the wear resistance.

[0070] (2) Tensile strength: tested according to standard ASTM D412.

[0071] (3) Elongation: Tested according to standard ASTM D412.

[0072] Table 1

[0073]

[0074]

[0075] It can be seen from the data in Table 1 that the silicone-modified polyurethane with wear-resistant effect obtained in the embodiment of the present invention is applied to TPU polymer materials, which can significantly improve the wear resistance of TPU and has good compatibility with TPU polymer materials. Using it as a wear-resistant agent can significantly improve the wear resistance of TPU and has less effect on the mechanical properties of TPU.

[0076] Among them, when the mass ratio between the polylactic acid polyol and the hydroxyl-containing organopolysiloxane prepolymer in the components is (5-7): (3-5), the organosilicon-modified polyurethane can obtain the best comprehensive performance.

[0077] The applicant declares that the present invention illustrates a kind of silicone-modified polyurethane with wear-resistant effect and its preparation method and application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A silicone-modified polyurethane for wear resistance, characterized in that: The organosilicon-modified polyurethane is obtained by reacting a reaction system comprising the following components: (a) polyisocyanates having at least two isocyanate groups; (b) a polymer polyol mixture consisting of polylactic acid polyol and a hydroxyl-containing silicone prepolymer; (c) chain extenders; (d) a capping agent having a long carbon chain hydrocarbon group, which has at least one isocyanate group-reactive group; The component (d) having a capping agent with a long carbon chain hydrocarbon group is a long carbon chain monofunctional amine compound; The mass ratio of the polylactic acid polyol to the hydroxyl-containing organopolysiloxane prepolymer in the component (b) is (5-7): (3-5); Based on 100 parts by weight of the total weight of the reaction system, the amount of the component (d) end-capping agent having a long carbon chain hydrocarbon group added is 7.5 to 15 parts by weight.

2. The organosilicon-modified polyurethane according to claim 1, characterized in that: The molar ratio between the isocyanate groups and the hydroxyl groups in the reaction system is 1.02 to 1.

2.

3. The organosilicon-modified polyurethane according to claim 1, characterized in that: Based on 100 parts by weight of the total weight of the reaction system, the added amount of the component (c) chain extender is 1 to 5 parts by weight.

4. The organosilicon-modified polyurethane according to claim 1, characterized in that: The component (d) end-capping agent having a long carbon chain hydrocarbon group includes aliphatic primary amines having 15 to 22 carbon atoms.

5. The organosilicon-modified polyurethane according to claim 1, characterized in that: The component (c) includes a dihydroxy chain extender and / or a trihydroxy chain extender.

6. The organosilicon-modified polyurethane according to claim 1, characterized in that: The molecular weight of the polylactic acid polyol is 1000-2000 g / mol.

7. The organosilicon-modified polyurethane according to claim 1, characterized in that: The hydroxyl-containing organopolysiloxane prepolymer includes a double-terminal monohydroxyl organosilicon prepolymer and / or a single-terminal dihydroxyl organosilicon prepolymer.

8. The organosilicon-modified polyurethane according to claim 1, characterized in that: The viscosity of the hydroxyl-containing organopolysiloxane prepolymer is 15-100 cps.

9. The method for preparing the organosilicon-modified polyurethane according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: S1. reacting component (a) a polyisocyanate having at least two isocyanate groups and component (b) a polymer polyol mixture to obtain a prepolymer; S2. After the prepolymer and the component (c) chain extender undergo a chain extension reaction, the prepolymer reacts with the component (d) end-capping agent, and then cools and crystallizes to obtain the organosilicon-modified polyurethane.

10. The method for preparing silicone-modified polyurethane according to claim 9, characterized in that: In step S1, the reaction temperature is 70-80° C. and the reaction time is 3-5 h.

11. The method for preparing silicone-modified polyurethane according to claim 9, characterized in that: The step S1 also includes a catalyst.

12. The method for preparing silicone-modified polyurethane according to claim 9, characterized in that: In step S2, the reaction time is 1 to 3 hours.

13. Use of the organosilicon-modified polyurethane according to any one of claims 1 to 8 or the organosilicon-modified polyurethane prepared by the preparation method according to any one of claims 9 to 12 in plastic products.

14. A wear-resistant agent, characterized in that: The wear-resistant agent comprises the organosilicon-modified polyurethane according to any one of claims 1 to 8 or the organosilicon-modified polyurethane prepared according to the preparation method according to any one of claims 9 to 12.

15. A modified TPU, characterized in that: The invention comprises a thermoplastic polyurethane elastomer and an anti-wear agent, wherein the anti-wear agent comprises the organosilicon-modified polyurethane according to any one of claims 1 to 8 or the organosilicon-modified polyurethane prepared by the preparation method according to any one of claims 9 to 12.

16. The modified TPU according to claim 15, characterized in that: Based on 100 parts by weight of the modified TPU, the modified TPU comprises 100 parts of thermoplastic polyurethane elastomer and 2-15 parts of wear-resistant agent.

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