Bio-based polyurethane beach protection material and preparation method thereof

Abstract

The invention discloses a bio-based polyurethane beach protection material and a preparation method thereof. The bio-based polyurethane beach protection material is prepared from bio-based polyurethane, solid granules and fiber filler. The biomass polyurethane is prepared through a reaction of a component A and a component B. The component A comprises bio-based polyol, a chain extender, a catalyst, a water removal agent and a coloring agent. Wherein the component A is isocyanate, the component B is isocyanate, and the isocyanate in the component B is isophorone isocyanate and polymethylene polyphenyl isocyanate (P-MDI); the solid granules comprise one or two of rock and coral sand; the fiber filler comprises one or two of glass fibers and basalt fibers. The bio-based polyurethane beach protection material and the preparation method thereof, disclosed by the invention, are particularly suitable for a protection material which is used for preventing scouring, dissipating waves, permeating water and easily adhering organisms on river and ocean beaches, and solve the structural and ecological environment problems of the beach protection material with a reinforced concrete structure at present.

Description

Technical Field

[0001] The invention relates to the field of ecological and environmentally friendly materials, and in particular to a bio-based polyurethane shore protection material and a preparation method thereof. Background Art

[0002] Beach protection is an engineering measure taken to protect the banks of rivers, lakes and seas from the invasion and scouring of water currents, wind and waves, and tides. Reinforced concrete building materials or components are usually laid directly on the waterside slopes of embankments or beaches to form a continuous covering layer to prevent erosion and scouring by water currents, wind and waves. However, there are some problems with commonly used concrete building materials in beach protection. Concrete structures have serious impacts on the ecology, hindering the attachment of organisms and the growth of plants, and are greatly affected by the impact of water currents. In particular, traditional beach protection of marine islands and reefs is very susceptible to damage from the impact of waves, and seriously affects the habitat of marine life.

[0003] Polyurethane materials have been used in road repair and other aspects. Currently on the market, there are permeable pavement materials made of crushed stone or stone rice bonded with binders. The binder is made by reacting polyether polyol and isocyanate curing agent. The advantage of this system is that the water permeability and porosity are significantly increased, but the aging resistance of these permeable pavement materials is poor.

[0004] Patent CN 114716957 discloses a non-yellowing polyurethane two-component adhesive for permeable pavement, which is suitable for sponge city permeable pavement and urban slow lane stone bonding, as well as various recyclable solid waste aggregate bonding, but the strength is not high. CN118668548A discloses a high-performance polyurethane mixture pavement structure and its construction method, including a base layer, a sealing layer, a cushion layer, a second bonding layer and a polyurethane surface layer, which is not suitable for shore protection. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a bio-based polyurethane shore protection material and a preparation method to solve the problems of poor ecological and environmental protection, inability to attach organisms, and serious damage caused by water flow impact of existing shore protection materials.

[0006] In order to solve the above technical problems, the technical solution of the present invention is as follows:

[0007] A bio-based polyurethane shore protection material, characterized by comprising the following preparation raw materials:

[0008] 100 parts by weight of bio-based polyurethane, 300-1000 parts by weight of solid granules, and 5-50 parts by weight of fiber filler;

[0009] Furthermore, the biomass polyurethane is synthesized by reacting component A and component B;

[0010] Further, the component A includes a bio-based polyol, a chain extender, a catalyst, a water remover, and a colorant; wherein the bio-based polyol is a plant oil polyol with a hydroxyl value of 120-180 mgKOH / g; wherein the chain extender is any one of dipropylene glycol and trimethylolpropane; wherein the catalyst is any one of dibutyltin dilaurate and stannous octoate; wherein the water remover is any one of AdditiveOF and 3A molecular sieve; wherein the colorant is a black slurry;

[0011] Further, the B component is an isocyanate; wherein the isocyanate is a combination of isophorone isocyanate and polymethylene polyphenyl polyisocyanate (P-MDI);

[0012] Furthermore, the component A and the component B of the bio-based polyurethane are reacted according to a molar ratio of hydroxyl functional groups in the component A to isocyanate functional groups in the component B of 1:1.1-1.3 to prepare the bio-based polyurethane;

[0013] Furthermore, the solid granular material is one of rock and coral sand or a mixture of the two;

[0014] Furthermore, the fiber filler is one of silanized modified glass fiber and basalt fiber, or a mixture of the two.

[0015] Furthermore, the component A of the bio-based polyurethane comprises the following components in parts by weight:

[0016] Bio-based polyol: 100 parts; chain extender: 1-5 parts; catalyst: 0.02-0.2; water scavenger: 1-5 parts; colorant: 1-3 parts;

[0017] Furthermore, the component B of the bio-based polyurethane comprises the following components in parts by weight:

[0018] 20-50 parts of isophorone isocyanate;

[0019] Polymethylene polyphenyl polyisocyanate (P-MDI) 50-80 parts.

[0020] Furthermore, the weight ratio of the solid granular material to the coral sand is 80:20-100:0 based on the whole solid granular material.

[0021] Furthermore, the rock is graded gravel with a particle size of 3-8 mm; and the coral sand is large-particle coral sand after the powder is removed using a No. 8 sieve.

[0022] Furthermore, the fiber filler is one of glass fiber and basalt fiber, or a mixture of the two, with a length of 8-20 mm and a diameter of 10-100 μm and silanized.

[0023] Furthermore, in the fiber filler, based on the entire fiber filler, the weight ratio of glass fiber to basalt fiber is 20:80-80:20.

[0024] Furthermore, a method for preparing a bio-based polyurethane shore protection material further comprises the steps of preparing a component A of the bio-based polyurethane and a component B of the bio-based polyurethane:

[0025] (1) heating a selected amount of bio-based polyol at 110° C. for vacuum dehydration to a water content of less than 0.3%, then cooling to 30-50° C., adding a certain weight portion of a chain extender, a catalyst, a dehydrating agent and a colorant, and fully stirring and mixing to obtain component A of the bio-based polyurethane;

[0026] (2) mixing a selected amount of isophorone isocyanate and polymethylene polyphenyl polyisocyanate to obtain a component B of the bio-based polyurethane;

[0027] A method for preparing a bio-based polyurethane shore protection material, the method comprising the following steps:

[0028] Step 1: According to the molar ratio of the hydroxyl functional group in component A to the isocyanate functional group in component B, component A and component B are mixed and stirred to prepare a bio-based polyurethane material;

[0029] Step 2: adding a certain weight portion of the fiber filler to the bio-based polyurethane material prepared in step 1 after drying, and stirring and mixing thoroughly to obtain a bio-based polyurethane fiber mixture material;

[0030] Step 3: adding a certain weight portion of dry solid pellets into a mixer and stirring, and then adding the bio-based polyurethane fiber mixture obtained in step 2 into the solid pellet mixer and stirring evenly to obtain an uncured beach protection material;

[0031] Step 4: The uncured shore protection material obtained in step 3 is piled and compacted according to the shore protection shape requirements, and the shore protection material is obtained after it is completely cured and formed.

[0032] The present invention discloses a bio-based polyurethane shore protection material and a preparation method thereof, wherein the bio-based polyurethane shore protection material is prepared from bio-based polyurethane, solid granules and fiber fillers. The biomass polyurethane is prepared by reacting component A and component B, wherein the component A includes bio-based polyol, chain extender, catalyst, dewatering agent and colorant; wherein the component B includes the isocyanate isophorone isocyanate and polymethylene polyphenyl polyisocyanate (P-MDI); the solid granules include one or two of rock and coral sand; the fiber filler includes one or two of glass fiber and basalt fiber. The bio-based polyurethane shore protection material and the preparation method thereof disclosed in the present invention are particularly suitable for anti-scouring, wave-breaking, water-permeable and easy-to-biologically-attached protective materials for rivers and ocean beaches, and solve the structural and ecological environmental problems existing in the shore protection materials of reinforced concrete structures at present.

[0033] The beneficial effects of the present invention are:

[0034] (1) The bio-based polyurethane used in the present invention is a bio-based polyol derived from plant sources such as castor oil and soybean oil, which can improve the biological adhesion of beach protection materials, is green and environmentally friendly, and solves the structural and ecological environmental problems of current reinforced concrete protection materials.

[0035] (2) The bio-based polyurethane used in the present invention reacts with fiber fillers and rock and / or coral sand solid particles. Due to the addition of glass fiber and basalt fiber fillers modified with silane coupling agents that are highly compatible with the bio-based polyurethane and solid particles, the structural strength of the shore protection material is enhanced. In addition, the use of rock and coral sand composites can make full use of local beach resources, which is particularly beneficial for offshore island and reef beach protection.

[0036] (3) The bio-based polyurethane beach protection material prepared by the present invention has a porous property. On the one hand, it is convenient for the attachment and growth of beach biological resources. On the other hand, the porous beach protection material can effectively reduce the impact of waves, play a role in dissipating waves and energy, and reduce the damage caused by wave impact. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described in conjunction with specific embodiments below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. The following embodiments are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention. 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.

[0039] Example

[0040] Examples 1-4 prepared the bio-based polyurethane beach protection material according to the following steps:

[0041] Step 1: mixing a certain weight portion of a bio-based polyurethane component A and a component B according to a selected amount ratio to obtain a bio-based polyurethane material;

[0042] Step 2: adding a certain weight portion of the fiber filler to the bio-based polyurethane material prepared in step 1 after drying, and stirring and mixing thoroughly to obtain a bio-based polyurethane fiber mixture material;

[0043] Step 3: adding a certain weight portion of dry solid pellets into a mixer and stirring, and then adding the bio-based polyurethane fiber mixture obtained in step 2 into the solid pellet mixer and stirring evenly to obtain an uncured beach protection material;

[0044] The uncured shore protection material obtained in step 3 is piled and compacted according to the shore protection shape requirements, and the shore protection material is obtained after it is completely cured and formed.

[0045] The weight proportions of the components for preparing bio-based polyurethane are shown in Table 1 unless otherwise specified.

[0046] Table 1

[0047]

[0048] Bio-based polyol 1: Bio-based polyol derived from castor oil, hydroxyl value 130±20 mgKOH / g, acid value ≤1.0 mgKOH / g, viscosity 1500±300cps@25℃;

[0049] Bio-based polyol 2: Bio-based polyol derived from soybean oil, hydroxyl value 150±10 mgKOH / g, acid value ≤1.0 mgKOH / g, viscosity 1000±200cps@25℃;

[0050] Polyol 94: 94 parts by weight of polyether polyol 2000 of chemical origin.

[0051] Chain extender 1: dipropylene glycol; Chain extender 2: trimethylolpropane;

[0052] Catalyst 1: dibutyltin dilaurate; Catalyst 2: stannous octoate;

[0053] Defoamer: silicone defoamer;

[0054] Dehydrating agent 1: 3A molecular sieve; Dehydrating agent 2: Additive OF;

[0055] Colorant: Black paste

[0056] Isocyanate 1: isophorone isocyanate;

[0057] Isocyanate 2: polymethylene polyphenyl polyisocyanate PM-200;

[0058] The weight proportions of the components of the bio-based polyurethane beach protection material are shown in Table 2, unless otherwise specified.

[0059] Table 2

[0060]

[0061] Glass fiber: 15 micron diameter, 18 mm length chopped yarn, surface silane modified;

[0062] Basalt fiber: diameter 20 microns, length 18 mm chopped yarn, surface silane modified;

[0063] Graded crushed stone: 3-8mm graded rock;

[0064] Coral sand: coral fragments with a particle size greater than 3mm and a maximum length less than 20mm;

[0065] Comparative Examples 1, 2

[0066] Comparative Example The preparation steps of Reference Example 1-4 were implemented, wherein the components of the polyurethane material are shown in Table 1, and the prepared shore protection material is shown in Table 2.

[0067] The performance of the shore protection materials of the embodiments and comparative embodiments is shown in Table 3.

[0068] Table 3

[0069]

[0070] From the comparison summary of Tables 1-3, it can be seen that the bio-based polyurethane shore protection material used in the embodiment enhances the mechanical properties and biological adhesion of the shore protection material through the combined action of bio-based polyurethane, solid granules and fiber fillers, and has a higher porosity, which promotes the wave dissipation, energy absorption and ecological performance of the shore protection material. Compared with the comparative example, it has better structural performance and biological adhesion, and is more ecological and environmentally friendly.

[0071] Finally, the above are only preferred embodiments of the present invention and are not intended to limit the protection scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A bio-based polyurethane beach protection material, characterized in that: The preparation includes the following raw materials: 100 parts by weight of bio-based polyurethane, 300-1000 parts by weight of solid granules, and 5-50 parts by weight of fiber filler; The biomass polyurethane is synthesized by reacting component A and component B; The component A includes a bio-based polyol, a chain extender, a catalyst, a water remover, and a colorant; wherein the bio-based polyol is a plant oil polyol with a hydroxyl value of 120-180 mgKOH / g; wherein the chain extender is any one of dipropylene glycol and trimethylolpropane; wherein the catalyst is any one of dibutyltin dilaurate and stannous octoate; wherein the water remover is any one of AdditiveOF and 3A molecular sieve; wherein the colorant is a black slurry; The B component is an isocyanate; wherein the isocyanate is a combination of isophorone isocyanate and polymethylene polyphenyl polyisocyanate (P-MDI); The component A and the component B of the bio-based polyurethane are reacted according to a molar ratio of the hydroxyl functional group in the component A to the isocyanate functional group in the component B of 1:1.1-1.3 to prepare the bio-based polyurethane; The solid granular material is one of rock and coral sand or a mixture of the two; The fiber filler is one of silanized modified glass fiber and basalt fiber or a mixture of the two.

2. The bio-based polyurethane beach protection material according to claim 1, characterized in that: Component A of the bio-based polyurethane comprises the following components in parts by weight: Bio-based polyols: 100 parts; Chain extender: 1-5 parts; Catalyst: 0.02-0.2; Dewatering agent: 1-5 parts; Colorant: 1-3 parts; The component B of the bio-based polyurethane comprises the following components in parts by weight: 20-50 parts of isophorone isocyanate; Polymethylene polyphenyl polyisocyanate (P-MDI) 50-80 parts.

3. The bio-based polyurethane beach protection material according to claim 1, characterized in that: The weight ratio of the solid granular material to the coral sand is 80:20-100:0 based on the whole solid granular material.

4. A bio-based polyurethane beach protection material according to claim 1 and claim 3, characterized in that: The rock is graded gravel with a particle size of 3-8 mm; the coral sand is large-particle coral sand after the powder is removed by using a No. 8 sieve.

5. The bio-based polyurethane shore protection material according to claim 1, characterized in that: The fiber filler is one of glass fiber and basalt fiber or a mixture of the two, which has a length of 8-20 mm and a diameter of 10-100 μm and has been silanized and modified.

6. A bio-based polyurethane beach protection material according to claims 1 and 5, characterized in that: The fiber filler, based on the entire fiber filler, has a weight ratio of glass fiber to basalt fiber of 20:80-80:

20.

7. A method for preparing a bio-based polyurethane beach protection material according to any one of claims 1 to 6, characterized in that: The method further comprises the steps of preparing component A of bio-based polyurethane and component B of bio-based polyurethane: A selected amount of bio-based polyol is heated to 110°C for vacuum dehydration to a water content of <0.3%, then cooled to 30-50°C, and a certain weight portion of chain extender, catalyst, dehydrating agent and colorant are added, and the mixture is stirred and mixed thoroughly to obtain component A of bio-based polyurethane; The selected amount of isophorone isocyanate and polymethylene polyphenyl polyisocyanate are mixed to obtain the B component of the bio-based polyurethane.

8. A method for preparing a bio-based polyurethane beach protection material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: Step 1: According to the molar ratio of the hydroxyl functional group in component A to the isocyanate functional group in component B, component A and component B are mixed and stirred to prepare a bio-based polyurethane material; Step 2: adding a certain weight portion of the fiber filler to the bio-based polyurethane material prepared in step 1 after drying, and stirring and mixing thoroughly to obtain a bio-based polyurethane fiber mixture material; Step 3: adding a certain weight portion of dry solid pellets into a mixer and stirring, and then adding the bio-based polyurethane fiber mixture obtained in step 2 into the solid pellet mixer and stirring evenly to obtain an uncured shore protection material; Step 4: The uncured shore protection material obtained in step 3 is piled and compacted according to the shore protection shape requirements, and the bio-based polyurethane shore protection material is obtained after it is completely cured and formed.

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