Low-density rapid-forming polyurethane foam filling material for kayaks and preparation method thereof

Abstract

The present invention belongs to the technical field of polyurethane foam filling materials, and specifically relates to a low-density rapid prototyping polyurethane foam filling material for kayaks and a preparation method thereof. The low-density rapid prototyping polyurethane foam filling material for kayaks described in the present invention is made of component A and component B in a weight ratio of 1: (0.8-1.1); component A comprises: trishydroxyethyl isocyanurate polyol A, polyether polyol B, polyether polyol C, foam stabilizer, toughening agent, catalyst, and foaming agent; component B comprises: diphenylmethane diisocyanate and toughening agent. The low-density rapid prototyping polyurethane foam filling material for kayaks of the present invention has good filling properties, excellent bonding properties, and no shelling and filling defects. The present invention also provides a preparation method thereof, which has simple process, easy operation, low volatility, and no three wastes, and is suitable for kayaks.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane foam filling materials, and particularly relates to a low-density rapid-forming polyurethane foam filling material for kayaks and a preparation method thereof. Background Art

[0002] Kayaking is gaining popularity in China. Rigid kayaks offer a more dynamic and dynamic ride, and their rigid bodies repel water, preventing them from effectively adhering to the hull. This provides a more engaging and engaging experience, leading to a relatively broad market for rigid kayaks. As a water sport, kayaks have high requirements, requiring low weight and excellent dimensional stability. Furthermore, kayaks come in a variety of shapes and sizes, varying significantly depending on the desired experience. Ensuring rapid molding of the filling material while ensuring effective filling at the varying corners and strong adhesion between the filling material and the kayak's rigid shell creates a unified whole is crucial. While rigid polyurethane foam offers advantages such as light weight, excellent dimensional stability, and ease of molding, it can also exhibit filling defects in corners and the lack of adhesion between the foam and the rigid shell.

[0003] CN103818068A discloses a method for producing functional structural lightweight materials using polymer chemical materials. Component A includes polyols, chain extenders, foaming agents, blowing agents, catalysts, flame retardants, fillers and antistatic materials, which are respectively made into surface layer, middle layer and outer layer. Component B includes isocyanate, epoxy resin, coloring material, which are respectively made into surface layer, middle layer and outer layer. Component A and component B are mixed in a weight ratio of 1: (1-2) and injected into a mold, and compression molding is performed to obtain the desired product. After the inner surface layer A / B components are injected in a 1:1 ratio, the density can be as high as 600kg / m 3 After the middle layer A / B components are injected at a ratio of 1:1.1, the density can reach up to 300kg / m 3 After the A / B components of the outer layer are injected at a ratio of 1:1, the density can reach up to 800kg / m 3 The preparation process is complicated and the materials need to be stacked in layers. Summary of the Invention

[0004] The present invention aims to provide a low-density rapid-forming polyurethane foam filling material for kayaks, which has good filling properties, excellent bonding properties, and no shelling or filling defects. The present invention also provides a preparation method thereof, which has a simple process, is easy to operate, has low volatility, and is free of three wastes, and is suitable for kayaks.

[0005] The low-density rapid-forming polyurethane foam filling material for kayaks of the present invention is made of component A and component B in a weight ratio of 1: (0.8-1.1), preferably 1:1;

[0006] In terms of weight percentage, component A is:

[0007]

[0008]

[0009] In terms of weight percentage, component B is:

[0010] Diphenylmethane diisocyanate 90-95%,

[0011] Toughening agent 5-10%;

[0012] Diphenylmethane diisocyanate is preferably produced by Wanhua Chemical, brand PM200.

[0013] Polyether polyol B is a polypropylene oxide ether polyol with an average functionality of 7 to 8 and a hydroxyl value of 400 to 450. Polyether polyol B is a special polyether polyol that needs to be customized according to the hydroxyl value and average functionality provided by the present invention.

[0014] The polyether polyol C is a polyether polyol having an average functionality of 2, a hydroxyl value of 109-115 mgKOH / g, a viscosity of 1200-1600 mPa·s at 25° C., and an initiator of bisphenol A. The polyether polyol C is preferably INOVOL S210H produced by Shandong Yinuowei New Materials Co., Ltd.

[0015] The preparation method of trishydroxyethyl isocyanurate polyol A comprises the following steps: adding water to trishydroxyethyl isocyanurate, stirring and dissolving the mixture to obtain an aqueous solution of trishydroxyethyl isocyanurate; then adding a mixed solution of acetone and phosphoric acid, stirring uniformly, heating the mixture to 90-95° C., filtering the mixture in a circulating manner to remove water and acetone, and drying the mixture to a moisture content of 0.01-0.04 wt %; adding a DMC catalyst under nitrogen protection, heating the mixture to 127-133° C., evacuating the mixture to -0.096-0.08 MPa, bubbling nitrogen for 5-7 hours, adding propylene oxide to initiate a reaction, and continuously adding propylene oxide dropwise after the pressure drops to 0.02-0.03 MPa to carry out continuous polymerization. After the reaction is completed, evacuating the mixture for 3-5 hours to obtain trishydroxyethyl isocyanurate polyol A having a hydroxyl value of 386-445 mgKOH / g.

[0016] The added mass of the DMC catalyst is 0.005-0.006% of trishydroxyethyl isocyanurate, and the mass ratio of propylene oxide to trishydroxyethyl isocyanurate is 1:1.5-1:2.3.

[0017] The foam stabilizer is one or both of organosilicon stabilizers B84813 and H36813. H36813 is preferably produced by Zhongshan Dongjun Chemical Co., Ltd.

[0018] The toughening agent is one or more of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol monobutyl ether, and N-methyl pyrrolidone.

[0019] The catalyst is a combination of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, benzylamine, delayed quaternary ammonium salt catalyst TMR-2, and 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine.

[0020] The foaming agent is a combination of water, foaming agent HFC-245fa, cyclopentane, normal pentane and isopentane.

[0021] The method for preparing the low-density rapid prototyping polyurethane foam filling material for kayaks of the present invention comprises the following steps:

[0022] (1) Component A: First, add tris(hydroxyethyl)isocyanurate polyol A, polyether polyol B, and polyether polyol C based on the formula amount into a reaction kettle and stir, then add foam stabilizer, toughening agent, catalyst, and finally add foaming agent, and stir and react at room temperature for 2-3 hours to obtain component A;

[0023] (2) Component B: Add diphenylmethane diisocyanate into a reaction kettle, then add a toughening agent, and stir the reaction at room temperature for 0.5 to 1 hour to obtain component B;

[0024] (3) When using, mix component A and component B in a mass ratio of 1: (0.8-1.1) and mix them evenly according to the injection density of 30-35kg / m 3 , injected into the mold, and after 5 to 7 minutes of molding and maturation, a low-density rapid molding polyurethane foam filling material for kayaks is obtained.

[0025] The low-density rapid prototyping polyurethane foam filling material for kayaks of the present invention is used as a kayak. First, the A component of the present invention adopts trihydroxyethyl isocyanurate polyol A, which achieves the tricyclic isocyanurate structure possessed by the high-material ratio system at a lower density and lower material ratio than that used for kayaks. At the same time, it is matched with the high-functional polyether polyol of the present invention, which has good dimensional stability and better demoulding properties. Then, the polyether polyol C in the combination material A of the present invention adopts a polyether polyol with high molecular weight bisphenol A as the initiator. At the same time, the benzene ring structure of bisphenol A has good mutual solubility with the B material of the composition, and the foam is fine. It is matched with special silicone oil to ensure the filling performance during foaming in a mold with a variable shape and avoid filling defects. In addition, the present invention introduces a toughening agent into the A and B components to reduce the surface tension of the configured combination material, improve the foam toughness and bonding performance, avoid environmental pollution caused by spreading glue, and is more environmentally friendly. Finally, the present invention prepares a low-density rapid-forming polyurethane foam filling material for kayaks by combining the polyether polyol system, catalyst, toughening agent, and foaming agent components in a suitable proportion.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The low-density rapid prototyping polyurethane foam filling material for kayaks prepared by the present invention is prepared by mixing the traditional A component and B component in a ratio of 1:1.2 and a density of 40-45 kg / m 3 Compared with the injection density, the 10min molding process is better at 1: (0.8-1.1) material ratio, 30-35kg / m 3 Rapid molding within 5 to 7 minutes at injection density yields products with good dimensional stability and stable product quality, with dimensional stability within 1.0%. At the same time, the products have good filling and excellent bonding properties, and are free of shelling and filling defects.

[0028] (2) The method for preparing the low-density rapid prototyping polyurethane foam filling material for kayaks of the present invention has the advantages of simple process, easy operation, low volatility, no three wastes, low production cost and high production efficiency. At the same time, the process of further preparing the kayak is also carried out at room temperature and normal pressure, which is simple and easy to operate. DETAILED DESCRIPTION

[0029] The present invention is described below with reference to the following embodiments, but the present invention is not limited thereto.

[0030] The following weight percentages are by mass. All unspecified raw materials or additives were obtained from normal commercial sources. Diphenylmethane diisocyanate was produced by Wanhua Chemical Group, brand PM200. Polyether polyol C was INOVOL S210H from Shandong Yinuowei New Materials Co., Ltd. Polyether polyol R8345 has a functionality of 4.6 and a hydroxyl value of 450±15, and is manufactured by Shandong Yinuowei New Materials Co., Ltd.; polyether polyol C210 has a functionality of 2 and a hydroxyl value of 112±3, and is manufactured by Shandong Yinuowei New Materials Co., Ltd.

[0031] The following tris(hydroxyethyl)isocyanurate polyol A was prepared by the following preparation method: 524g of tris(hydroxyethyl)isocyanurate was added to a 2L autoclave at room temperature, followed by addition of 200g of distilled water, stirring and dissolving to obtain an aqueous solution of tris(hydroxyethyl)isocyanurate, followed by addition of 600g of acetone and a mixed solution of 0.03g of 85wt% phosphoric acid, stirring evenly, then heating to 90°C, circulating filtration, vacuuming to remove moisture and acetone, and drying to a moisture content of 0.03wt%; adding 0.2g of DMC catalyst under a nitrogen atmosphere, heating to 127°C and then vacuuming to -0.096MPa, bubbling nitrogen for 5h, then adding 30g of propylene oxide to initiate the reaction, and continuously adding the remaining 228g of propylene oxide to carry out continuous polymerization when the reactor pressure drops to 0.02MPa. After the reaction is completed, vacuuming and stripping the monomers for 3h to obtain tris(hydroxyethyl)isocyanurate polyol A having a hydroxyl value of 430±3mgKOH / g.

[0032] Example 1

[0033] In terms of weight percentage, component A is:

[0034]

[0035] Polyether polyol B is a polypropylene oxide ether polyol having an average functionality of 8 and a hydroxyl value of 400;

[0036] In terms of weight percentage, component B is:

[0037] Diphenylmethane diisocyanate 95%,

[0038] Diethylene glycol ethyl ether acetate 5%;

[0039] The method for preparing the low-density rapid prototyping polyurethane foam filling material for kayaks comprises the following steps:

[0040] (1) Component A: First, add tris(hydroxyethyl)isocyanurate polyol A, polyether polyol B, and polyether polyol C based on the formula amount into a reaction kettle and stir, then add foam stabilizer, toughening agent, catalyst, and finally add foaming agent, and stir and react at room temperature for 3 hours to obtain component A;

[0041] (2) Component B: Add diphenylmethane diisocyanate into a reaction kettle, then add a toughening agent, and stir the reaction at room temperature for 0.5 h to obtain component B;

[0042] (3) When using, mix component A and component B in a mass ratio of 1:1 and mix them evenly according to the injection density of 32kg / m 3 , injected into the mold, and after 5 minutes of molding and maturation, a low-density rapid molding polyurethane foam filling material for kayaks was obtained.

[0043] Example 2

[0044] In terms of weight percentage, component A is:

[0045]

[0046] Polyether polyol B is a polypropylene oxide ether polyol having an average functionality of 7 and a hydroxyl number of 450;

[0047] In terms of weight percentage, component B is:

[0048]

[0049] The method for preparing the low-density rapid prototyping polyurethane foam filling material for kayaks comprises the following steps:

[0050] (1) Component A: First, add tris(hydroxyethyl)isocyanurate polyol A, polyether polyol B, and polyether polyol C based on the formula amount into a reaction kettle and stir, then add foam stabilizer, toughening agent, catalyst, and finally add foaming agent, and stir and react at room temperature for 2 hours to obtain component A;

[0051] (2) Component B: Add diphenylmethane diisocyanate into a reaction kettle, then add a toughening agent, and stir the reaction at room temperature for 0.5 h to obtain component B;

[0052] (3) When using, mix component A and component B in a mass ratio of 1:0.8 and pour at a density of 35kg / m 3 , injected into the mold, and after 6 minutes of molding and maturation, a low-density rapid molding polyurethane foam filling material for kayaks was obtained.

[0053] Example 3

[0054] In terms of weight percentage, component A is:

[0055]

[0056] Polyether polyol B is a polypropylene oxide ether polyol with an average functionality of 7.5 and a hydroxyl value of 430;

[0057] In terms of weight percentage, component B is:

[0058] Diphenylmethane diisocyanate 92%,

[0059] Diethylene glycol ethyl ether acetate 4%,

[0060] N-methylpyrrolidone 4%,

[0061] The method for preparing the low-density rapid prototyping polyurethane foam filling material for kayaks comprises the following steps:

[0062] (1) Component A: First, add tris(hydroxyethyl)isocyanurate polyol A, polyether polyol B, and polyether polyol C based on the formula amount into a reaction kettle and stir, then add foam stabilizer, toughening agent, catalyst, and finally add foaming agent, and stir and react at room temperature for 2 hours to obtain component A;

[0063] (2) Component B: Add diphenylmethane diisocyanate into a reaction kettle, then add a toughening agent, and stir the reaction at room temperature for 0.5 h to obtain component B;

[0064] (3) When using, mix component A and component B in a mass ratio of 1:1.1 and pour the material at a density of 30 kg / m 3 , injected into the mold, and after 7 minutes of molding and maturation, a low-density rapid molding polyurethane foam filling material for kayaks was obtained.

[0065] Example 4

[0066] The low-density rapid-molding polyurethane foam filling material for kayaks is made of component A and component B in a weight ratio of 1:1;

[0067] In terms of weight percentage, component A is:

[0068]

[0069] Polyether polyol B is a polypropylene oxide ether polyol having an average functionality of 8 and a hydroxyl value of 400;

[0070] In terms of weight percentage, component B is:

[0071]

[0072] The method for preparing the low-density rapid prototyping polyurethane foam filling material for kayaks comprises the following steps:

[0073] (1) Component A: First, add tris(hydroxyethyl)isocyanurate polyol A, polyether polyol B, and polyether polyol C based on the formula amount into a reaction kettle and stir, then add foam stabilizer, toughening agent, catalyst, and finally add foaming agent, and stir and react at room temperature for 2 hours to obtain component A;

[0074] (2) Component B: Add diphenylmethane diisocyanate into a reaction kettle, then add a toughening agent, and stir the reaction at room temperature for 0.5 h to obtain component B;

[0075] (3) When using, mix component A and component B in a mass ratio of 1:1 and mix them evenly according to the injection density of 32kg / m 3, injected into the mold, and after 7 minutes of molding and maturation, a low-density rapid molding polyurethane foam filling material for kayaks was obtained.

[0076] Comparative Example 1

[0077] Compared with Example 1, the only difference in this comparative example is that polyether polyol A and polyether polyol B are replaced with polyether polyol R8345, and the added mass is equal to the total amount of polyether polyol A and polyether polyol B in Example 1. When used, component A and component B are mixed uniformly in a mass ratio of 1:1, and the injection density is 32 kg / m 3 , injected into the mold, and after 10 minutes of molding and maturation, the polyurethane foam filling material is obtained.

[0078] Comparative Example 2

[0079] Compared with Example 2, the only difference in this comparative example is that polyether polyol A and polyether polyol B are replaced with polyether polyol R8345, and the added mass is equal to the total amount of polyether polyol A and polyether polyol B in Example 1. When used, component A and component B are mixed uniformly at a mass ratio of 1:1.2, and the injection density is 40.5 kg / m 3 , injected into the mold, and after 10 minutes of molding and maturation, the polyurethane foam filling material is obtained.

[0080] Comparative Example 3

[0081] The only difference between this comparative example and Example 3 is that polyether polyol C is replaced with polyether polyol C210, and the added mass is equal to that of polyether polyol C in Example 3; silicone oil B84813 and H36813 are replaced with silicone oil H3565, and the added amount is equal to the total amount of silicone oil B84813 and H36813 in Example 3. When using, component A and component B are mixed uniformly at a mass ratio of 1:1.1, and the injection density is 30 kg / m 3 , injected into the mold, and after 7 minutes of molding and maturation, a low-density rapid molding polyurethane foam filling material for kayaks was obtained.

[0082] Comparative Example 4

[0083] In terms of weight percentage, component A is:

[0084]

[0085] Polyether polyol B is a polypropylene oxide ether polyol having an average functionality of 8 and a hydroxyl value of 400;

[0086] In terms of weight percentage, component B is:

[0087] Diphenylmethane diisocyanate 100%

[0088] (1) Component A: First, add tris(hydroxyethyl)isocyanurate polyol A, polyether polyol B, and polyether polyol C based on the formula amount into a reaction kettle and stir, then add foam stabilizer, toughening agent, catalyst, and finally add foaming agent, and stir and react at room temperature for 3 hours to obtain component A;

[0089] (2) Component B: Add diphenylmethane diisocyanate into a reaction kettle, then add a toughening agent, and stir the reaction at room temperature for 0.5 h to obtain component B;

[0090] (3) When using, mix component A and component B in a mass ratio of 1:1 and mix them evenly according to the injection density of 43kg / m 3 , injected into the mold, and after molding and maturation, the polyurethane foam filling material is obtained.

[0091] Comparative Example 5

[0092] The only difference between this comparative example and Example 1 is that only N,N-dimethylcyclohexylamine is used as the catalyst, and the added mass is equal to the total amount of the catalyst in Example 1.

[0093] Comparative Example 6

[0094] The only difference between this comparative example and Example 1 is that only 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine is used as the catalyst, and the added mass is equal to the total amount of the catalyst in Example 1.

[0095] The polyurethane foam materials prepared in Examples 1-4 and Comparative Examples 1-6 were subjected to performance tests. The test results are shown in Table 1.

[0096] Table 1 Performance test results of polyurethane foams prepared in Examples 1-4 and Comparative Examples 1-6

[0097]

[0098]

[0099] As can be seen from Table 1, the polyurethane foam filling material prepared by the present invention has fast molding, good dimensional stability, and excellent bonding properties. Compared with Example 1, Comparative Example 1 does not contain tris(hydroxyethyl)isocyanurate polyol A) and high-functionality polyether polyol B, resulting in poor foam dimensional stability and a long mold opening time. Compared with Example 2, Comparative Example 2 does not contain tris(hydroxyethyl)isocyanurate polyol A) and high-functionality polyether polyol B. Only by increasing the material ratio and increasing the foam core density can the same dimensional stability be achieved, but the mold opening time is long. Compared with Example 3, Comparative Example 3 uses conventional high-molecular-weight polyether and silicone oil, but its miscibility with material B and fluidity are worse than those of Example 3, resulting in filling defects. Compared with Example 1, Comparative Example 4 does not introduce a toughening agent, and the surface tension of the composite material is not improved. The foam has poor toughness and poor adhesion to the shell, and shelling occurs. Compared with Example 1, the use of a single catalyst in Comparative Examples 5 and 6 causes an imbalance in the front and back reactions, poor fluidity, and significant filling defects in the filling areas such as corners, resulting in a reduced proportion of the bonding area between the foam and the kayak shell.

[0100] Of course, the above contents are only preferred embodiments of the present invention and should not be considered as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples. Equivalent changes and improvements made by ordinary technicians in this technical field within the essential scope of the present invention should all fall within the scope of the patent of the present invention.

Claims

1. A low-density rapid prototyping polyurethane foam filling material for kayaks, characterized by: Made of component A and component B in a weight ratio of 1: (0.8-1.1); In terms of weight percentage, component A is: Trihydroxyethyl isocyanurate polyol A30~45%, Polyether polyol B20~30%, Polyether polyol C5~10%, Foam stabilizer 2-3%, Toughening agent 10-15%, Catalyst 2-4%, Foaming agent 10-15%; In terms of weight percentage, component B is: Diphenylmethane diisocyanate 90-95%, Toughening agent 5-10%; Polyether polyol B is a polypropylene oxide ether polyol having an average functionality of 7 to 8 and a hydroxyl value of 400 to 450; Polyether polyol C is a polyether polyol having an average functionality of 2, a hydroxyl value of 109 to 115 mgKOH / g, a viscosity of 1200 to 1600 mPa·s at 25° C., and an initiator of bisphenol A; The toughening agent is one or more of diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol monobutyl ether, and N-methyl pyrrolidone; The foam stabilizer is one or both of B84813 and H36813; The catalyst is a combination of pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, benzylamine, delayed quaternary ammonium salt catalyst TMR-2, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine or 2,4,6-tris(dimethylaminomethyl)phenol; The hydroxyl value of trishydroxyethyl isocyanurate polyol A is 386-445 mgKOH / g; The preparation method of trishydroxyethyl isocyanurate polyol A comprises the following steps: adding water to trishydroxyethyl isocyanurate, stirring and dissolving the mixture to obtain an aqueous solution of trishydroxyethyl isocyanurate; then adding a mixed solution of acetone and phosphoric acid, stirring evenly, heating the mixture to 90-95° C., filtering the mixture in a circulation manner to remove water and acetone, and drying the mixture to a moisture content of 0.01-0.04 wt %; adding a DMC catalyst under nitrogen protection, heating the mixture to 127-133° C., evacuating the mixture to -0.096-0.08 MPa, bubbling nitrogen for 5-7 hours, adding propylene oxide to initiate a reaction, and continuously adding propylene oxide dropwise until the pressure drops to 0.02-0.03 MPa to carry out continuous polymerization. After the reaction is completed, evacuating the mixture for 3-5 hours to obtain trishydroxyethyl isocyanurate polyol A having a hydroxyl value of 386-445 mgKOH / g.

2. The low-density rapid prototyping polyurethane foam filling material for kayaks according to claim 1, characterized in that: The added mass of DMC catalyst is 0.005-0.006% of tris(hydroxyethyl)isocyanurate, and the mass ratio of propylene oxide to tris(hydroxyethyl)isocyanurate is 1:1.5-1:2.

3.

3. The low-density rapid prototyping polyurethane foam filling material for kayaks according to claim 1, characterized in that: The foaming agent is a combination of water, HFC-245fa, cyclopentane, n-pentane and isopentane.

4. The method for preparing a low-density rapid prototyping polyurethane foam filling material for kayaks according to claim 1, characterized in that: Here are the steps: (1) Component A: First, add trihydroxyethyl isocyanurate polyol A, polyether polyol B, and polyether polyol C based on the formula amount into the reactor and stir, then add the foam stabilizer, toughening agent, catalyst, and finally add the foaming agent, and stir and react at room temperature for 2 to 3 hours to obtain component A; (2) Component B: Add diphenylmethane diisocyanate into the reactor, then add the toughening agent, and stir the reaction at room temperature for 0.5 to 1 hour to obtain component B; (3) When using, mix component A and component B in a mass ratio of 1: (0.8-1.1) and mix them evenly according to the injection density of 30-35 kg / m 3 , injected into the mold, formed and matured for 5 to 7 minutes, and the mold was opened to obtain a low-density rapid molding polyurethane foam filling material for kayaks.

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