1. A pouring type polyurethane composite material anti-collision fence for an underwater pier is arranged on the outer side of a lower part structure of the pier, and the outer layer of the anti-collision fence is a basalt fiber reinforced plastic sleeve which plays a shaping role; a polyurethane composite material buffer layer with a buffering effect is arranged between the basalt fiber reinforced plastic sleeve and the pier, and the fiber reinforced water glass modified polyurethane material is matched with stone for cast-in-place molding; the method is characterized in that: the polyurethane composite material buffer layer is formed by casting the component A, the component B and the component C in situ by matching with stone; wherein

The component A comprises: 87-94 parts of water glass, 5-2 parts of glycerol, 3-2 parts of triisopropanolamine, 4-1.5 parts of water and 1-0.5 part of antioxidant-264;

the component B comprises: 75-81 parts of PAPI, 15-12 parts of polyurethane prepolymer, 3-2 parts of dioctyl phthalate, 1-0.5 part of AUCAT-101 catalyst, 1-0.5 part of CUCAT-U2 catalyst, 1.5-1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 1-0.5 part of 8-hydroxyquinolinone mildew preventive;

the component C comprises: 10-20 parts of fiber bundles and 200-600 parts of stones.

2. The underwater pier pouring type polyurethane composite material anti-collision fence according to claim 1, characterized in that: the basalt fiber reinforced plastic sleeve is a sleeve device made of basalt fiber reinforced unsaturated polyester or epoxy resin, the thickness of the sleeve is 8-10 mm, and the diameter of the sleeve is determined by the specific situation of the diameter of an on-site pier.

3. The underwater pier pouring type polyurethane composite material anti-collision fence according to claim 1, characterized in that: the water glass in the component A is sodium silicate water glass, the modulus is 2.2-2.4, and the density is 1.4-1.5 g/cm³(20 ℃) and the baume degree is 48-52 degrees.

4. The underwater pier pouring type polyurethane composite material anti-collision fence according to claim 1, characterized in that: the preparation method of the polyurethane prepolymer in the component B comprises the following steps:

accurately weighing 100 parts of polyether polyol N220, dehydrating for 2 hours at 120 ℃ and-0.09 MPa, accurately adding 32.16-42.11 parts of MDI-100 diisocyanate when the temperature is reduced to 50 ℃, reacting for 30 minutes at 50 ℃, then heating to 80-82 ℃, reacting for 2.0 hours, vacuumizing and defoaming for 30 minutes until the reactant is colorless transparent liquid, and thus obtaining the polyurethane prepolymer with the-NCO content of 5-7%.

5. The underwater pier pouring type polyurethane composite material anti-collision fence according to claim 1, characterized in that: the PAPI is polyphenyl polymethylene polyisocyanate, and the mass content of-NCO groups is 31.1-31.5%.

6. The underwater pier pouring type polyurethane composite material anti-collision fence according to claim 4, wherein: the MDI-100 diisocyanate is 4, 4' -diphenylmethane diisocyanate, and the mass content of NCO groups is 33.6%; the polyether polyol N220 is polyether polyol with the average molecular weight of 2000.

7. The underwater pier pouring type polyurethane composite material anti-collision fence according to claim 1, characterized in that: the HyMax220 hydrolysis resistant agent in the component B is sold by Shanghai Langyi functional materials Co., Ltd; the AUCAT-101 catalyst and the CUCAT-U2 catalyst are produced by Guangzhou Youyun chemical materials, Inc.; the antioxidant-264 is commercially available 2, 6-di-tert-butyl-4-methylphenol; the Defom5500 antifoaming agent is produced by moderate chemistry Co., Ltd; the component C is formed by mixing one or two of glass fiber or basalt fiber with the fiber bundle being 8-10 mm, and the pebbles are formed by crushing granite, basalt and limestone natural stones with the diameter being 5-10 mm.

8. A method for preparing a cast polyurethane composite material anti-collision fence for an underwater pier as claimed in any one of claims 1 to 7, which comprises the following steps:

step one, preparation of a component A:

step 1: adding 1-0.5 part of antioxidant-264 into 3-2 parts of triisopropanolamine, adding 5-2 parts of glycerol, further stirring for dissolving, then adding 4-1.5 parts of water, and uniformly stirring for dissolving to obtain a mixed solution A1;

step 2: slowly adding the mixed solution A1 into 87-94 parts of water glass under the condition that the stirring speed is 30r/min, and continuously stirring for 20 minutes to obtain a component A for later use;

step two, preparing the component B:

adding 75-81 parts of PAPI into a mixing container, adding 15-12 parts of polyurethane prepolymer into the mixing container, and stirring and mixing uniformly at normal temperature; then sequentially adding 3-2 parts of dioctyl phthalate, 1-0.5 part of AUCAT-101 catalyst, 1-0.5 part of CUCAT-U2 catalyst, 1.5-1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 1-0.5 part of 8-hydroxyquinolinone mildew preventive, stirring and mixing uniformly at normal temperature, vacuumizing and defoaming until the mixed liquid is transparent to obtain a component B, filling dry nitrogen, sealing and storing for later use;

thirdly, preparing the underwater pier pouring type polyurethane composite material anti-collision fence:

step 1: enclosing a pier to be protected by using a basalt fiber reinforced plastic sleeve with the thickness of 8-10 mm, wherein the diameter of the sleeve is determined by the specific situation on site, and the seam is connected by a nylon wire;

step 2: the water between the basalt fiber reinforced plastic sleeve fence and the pier does not need to be pumped out completely and is put into: 200-600 parts of stones with the diameter of 5-10 mm, mixing 10-20 parts of fiber bundles into the stones, placing the stones and the fiber bundles, pouring 200 parts of a mixture of the component A and the component B by using a grouting machine, and continuously or intermittently pouring; or continuously mixing, pouring and molding by a large stone and liquid material mixer; and (3) curing the casting material for 2-3 min, and after further curing is completed for 48 hours, obtaining the underwater pier casting type polyurethane composite material anti-collision fence.

9. The method for preparing the underwater pier pouring type polyurethane composite material anti-collision fence according to claim 8, wherein the method comprises the following steps: the grouting machine is a mining pneumatic grouting pump produced by Shanxi solidification force novel material company Limited and has the model number of 2 ZBQ-8/10.

Background

The accidents of ship-bridge collision occur continuously all over the world, and the frequency of the accidents of ship-bridge collision is far higher than that of the accidents imagined by people. The ship impact is one of the main reasons for bridge collapse across the channel, and the resulting consequences are extremely serious: the ship damages people and loses life, thus causing the blockage of the navigation channel, the interruption of land traffic and the pollution to the environment of the water area. Therefore, it is very necessary to install the anti-collision facilities on the navigation bridge pier. At present, the types of pier anti-collision facilities at home and abroad are more, the basic principle of the pier anti-collision facilities is designed based on energy absorption and momentum buffering, and each kind of pier anti-collision facility has the characteristics and the use conditions. In particular, collision avoidance facilities can be divided into two broad categories: one is indirect, which is characterized in that: and an anti-collision facility is additionally arranged outside the bridge pier, so that the bridge pier does not directly receive force and can thoroughly avoid the problem of ship collision. Such as: pile group mode, thin-shell sand-building cofferdam mode, artificial island mode and the like, and is generally suitable for occasions with shallow water and better geological conditions. Indirect collision avoidance methods, while once and for all, can affect the course and are often abandoned because of high cost or inadequate conditions. The second is a direct formula, and is characterized in that: the impact force is directly acted on the pier after being buffered, such as a string protection mode, a buffer material facility mode, a buffer facility engineering mode, a fixed or floating type sleeve box anti-collision facility and the like. Generally, when the method is used in the occasions with narrow navigation channels and deep water, the construction cost is saved, and the civil engineering quantity is not large, so that the direct collision avoidance becomes a realistic method and is a collision avoidance type which is researched more in recent years.

The direct anti-collision facility commonly used in bridges in China in recent years is in the form of a steel structure jacket or a buoyancy tank. But the steel jacket box has higher rigidity, is easy to rust and has high manufacturing cost and maintenance cost. Experimental studies have demonstrated that fiber composite structures as energy absorbing elements have higher energy absorbing capacity than some commonly used metallic material structures and uniform crush load distribution. Therefore, it is necessary to perform necessary research and experiments on the fiber composite cushioning material.

Chinese patent CN111593691A discloses an anti-collision member for bridge pier based on FRP and polyurethane foam filled cellular rubber concrete, which comprises an FRP (material compounded by continuous fiber and thermosetting resin) sleeve, polyurethane foam and a rubber concrete layer. The polyurethane foam adopts the prefab, just can carry out pouring of rubber concrete according to certain rule installation on the pier, and the work progress is loaded down with trivial details. The anti-collision device can be applied to the collision avoidance of the piers of newly-built roads and waterway bridges. Is not suitable for collision avoidance with the piers of the built waterway bridge.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a pouring type polyurethane composite material anti-collision fence for an underwater pier and a preparation method thereof.

A pouring type polyurethane composite material anti-collision fence for an underwater pier is arranged on the outer side of a lower part structure of the pier, and the outer layer of the anti-collision fence is a basalt fiber reinforced plastic sleeve which plays a shaping role; a polyurethane composite material buffer layer with a buffering effect is arranged between the basalt fiber reinforced plastic sleeve and the pier, and the fiber reinforced water glass modified polyurethane material is matched with stone for cast-in-place molding; the method is characterized in that: the polyurethane composite material buffer layer is formed by casting the component A, the component B and the component C in situ by matching with stone; wherein

The component A comprises: 87-94 parts of water glass, 5-2 parts of glycerol, 3-2 parts of triisopropanolamine, 4-1.5 parts of water and 1-0.5 part of antioxidant-264;

the component B comprises: 75-81 parts of PAPI, 15-12 parts of polyurethane prepolymer, 3-2 parts of dioctyl phthalate, 1-0.5 part of AUCAT-101 catalyst, 1-0.5 part of CUCAT-U2 catalyst, 1.5-1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 1-0.5 part of 8-hydroxyquinolinone mildew preventive;

the component C comprises: 10-20 parts of fiber bundles and 200-600 parts of stones.

In a further preferred scheme, the basalt fiber reinforced plastic sleeve is a sleeve device prepared from basalt fiber reinforced unsaturated polyester or epoxy resin, the thickness of the sleeve is 8-10 mm, and the diameter of the sleeve is determined by the specific situation of the diameter of a site pier;

in a further preferred scheme, the water glass in the component A is sodium silicate water glass, the modulus is 2.2-2.4, and the density is 1.4-1.5 g/cm³(20 ℃) and the baume degree is 48-52 degrees.

In a further preferred scheme, the preparation method of the polyurethane prepolymer in the component B comprises the following steps:

accurately weighing 100 parts of polyether polyol N220, dehydrating for 2 hours at 120 ℃ and-0.09 MPa, accurately adding 32.16-42.11 parts of MDI-100 diisocyanate when the temperature is reduced to 50 ℃, reacting for 30 minutes at 50 ℃, then heating to 80-82 ℃, reacting for 2.0 hours, vacuumizing and defoaming for 30 minutes until the reactant is colorless transparent liquid, and thus obtaining the polyurethane prepolymer with the-NCO content of 5-7%.

In a further preferable scheme, the PAPI is polyphenyl polymethylene polyisocyanate, and the mass content of-NCO groups is 31.1-31.5%.

In a further preferable scheme, the MDI-100 diisocyanate is 4, 4' -diphenylmethane diisocyanate, and the mass content of NCO groups is 33.6 percent; the polyether polyol N220 is polyether polyol with the average molecular weight of 2000;

in a further preferable scheme, the HyMax220 hydrolysis resistant agent in the component B is sold by Shanghai Langyi functional materials Co.Ltd; the AUCAT-101 catalyst is produced by Guangzhou Youyun chemical materials Co.Ltd; the antioxidant-264 is commercially available 2, 6-di-tert-butyl-4-methylphenol; the Defom5500 antifoaming agent is produced by moderate chemistry Co., Ltd; the component C is formed by mixing one or two of glass fiber or basalt fiber with the fiber bundle being 8-10 mm, and the pebbles are formed by crushing natural stones such as granite, basalt and limestone with the diameter being 5-10 mm.

The preparation method of the underwater pier pouring type polyurethane composite material anti-collision fence comprises the following steps:

step one, preparation of a component A:

step 1: adding 1-0.5 part of antioxidant-264 into 3-2 parts of triisopropanolamine, adding 5-2 parts of glycerol, further stirring for dissolving, then adding 4-1.5 parts of water, uniformly stirring for dissolving, adding 5-2 parts of glycerol and 3-2 parts of triisopropanolamine, stirring for mixing and dissolving to obtain a mixed solution A1;

step 2: slowly adding the mixed solution A1 into 87-94 parts of water glass under the condition that the stirring speed is 30r/min, and continuously stirring for 20 minutes to obtain a component A for later use;

step two, preparing the component B:

adding 75-81 parts of PAPI into a mixing container, adding 15-12 parts of polyurethane prepolymer into the mixing container, and stirring and mixing uniformly at normal temperature; then sequentially adding 3-2 parts of dioctyl phthalate, 1-0.5 part of AUCAT-101 catalyst, 1-0.5 part of CUCAT-U2 catalyst, 1.5-1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 1-0.5 part of 8-hydroxyquinolinone mildew preventive, stirring and mixing uniformly at normal temperature, vacuumizing and defoaming until the mixed liquid is transparent to obtain a component B, filling dry nitrogen, sealing and storing for later use;

thirdly, preparing the underwater pier pouring type polyurethane composite material anti-collision fence:

step 1: enclosing a pier to be protected by using a basalt fiber reinforced plastic sleeve with the thickness of 8-10 mm, wherein the diameter of the sleeve is determined by the specific situation on site, and the seam is connected by a nylon wire;

step 2: the water between the basalt fiber reinforced plastic sleeve fence and the pier does not need to be pumped out completely and is put into: 200-600 parts of stones with the diameter of 5-10 mm, mixing 10-20 parts of fiber bundles into the stones, placing the stones and the fiber bundles, pouring 200 parts of a mixture of the component A and the component B by using a grouting machine, and continuously or intermittently pouring; or continuously mixing, pouring and molding by a large stone and liquid material mixer; and (3) curing the casting material for 2-3 min, and after further curing is completed for 48 hours, obtaining the underwater pier casting type polyurethane composite material anti-collision fence.

The grouting machine is a mining pneumatic grouting pump produced by Shanxi solidification force novel material company Limited and has the model number of 2 ZBQ-8/10.

Compared with the prior art, the invention has the following advantages:

firstly, the basalt fiber reinforced plastic sleeve is taken as the shell of the anti-collision device, not only is the forming device during construction, but also is the outer shell of the anti-collision device after forming, the operation of installing and detaching the template is omitted, and the rigidity and the toughness of the anti-collision material are enhanced. Meanwhile, the corrosion resistance of the basalt fiber reinforced plastic material in water is superior to that of steel and concrete materials, and the basalt fiber reinforced plastic material has better use durability.

Secondly, water in the basalt fiber reinforced plastic sleeve does not need to be completely emptied and completely pumped out during construction, the product can be directly cast and molded in a water-containing or extremely humid environment, and the strength of the cast and molded material is not influenced by the presence of the water. The cast-in-place molding is realized, the construction operation is simple and convenient, and the anti-collision performance is excellent.

Thirdly, the water glass is introduced to modify the polyurethane material, so that the rigidity of the polyurethane material is increased, meanwhile, the fiber material and the stones are used to form a framework of the anti-collision composite material buffer layer, so that the stress is effectively dispersed, the overall stability and the collision resistance of the anti-collision device are enhanced, and the force of ship collision can be more effectively borne.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Example 1

According to the underwater pier pouring type polyurethane composite material anti-collision fence, the anti-collision fence is arranged on the outer side of a lower structure of a pier, and the outer layer of the anti-collision fence is a basalt fiber reinforced plastic sleeve which plays a shaping role; a polyurethane composite material buffer layer with a buffering effect is arranged between the basalt fiber reinforced plastic sleeve and the pier, and the fiber reinforced water glass modified polyurethane material is matched with stone for cast-in-place molding;

the basalt fiber reinforced plastic sleeve is a sleeve device made of basalt fiber reinforced unsaturated polyester, epoxy resin, phenolic resin or a plurality of composite resins, the thickness of the sleeve is 8mm, and the diameter of the sleeve is determined by the specific conditions of a pier on site.

The polyurethane composite material buffer layer is formed by casting the component A, the component B and the component C in situ by matching with stone materials:

the component A comprises: 87 parts of water glass, 5 parts of glycerol, 3 parts of triisopropanolamine, 4 parts of water and 1 part of antioxidant-264;

the component B comprises: 75 parts of PAPI, 15 parts of polyurethane prepolymer, 3 parts of dioctyl phthalate, 1 part of AUCAT-101 catalyst, 1 part of CUCAT-U2 catalyst, 1.5 parts of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 1 part of 8-hydroxyquinolinone mildew preventive;

the component C comprises: 10 parts of fiber bundles and 200 parts of stones.

The water glass is sodium silicate water glass, the modulus is 2.2-2.4, and the density is 1.4-1.5 g/cm³(20 ℃) and the baume degree is 48-52 degrees.

The preparation method of the polyurethane prepolymer in the component B comprises the following steps:

accurately weighing 100 parts of polyether polyol N220, dehydrating for 2h under the conditions of 120 ℃ and-0.09 MPa, accurately adding 32.16 parts of MDI-100 diisocyanate when the temperature is reduced to 50 ℃, reacting for 30min at 50 ℃, then heating to 80-82 ℃, reacting for 2.0h, vacuumizing and defoaming for 30min until the reactant is colorless transparent liquid, and thus obtaining the polyurethane prepolymer with the-NCO content of 5%.

The PAPI is polyphenyl polymethylene polyisocyanate, and the mass content of-NCO groups is 31.1-31.5%; the MDI-100 is 4, 4' -diphenylmethane diisocyanate, and the mass content of-NCO groups is 33.6%; the polyether polyol N220 is polyether polyol with the average molecular weight of 2000; the HyMax220 hydrolysis resistant agent is sold by Shanghai Langyi functional materials Co.Ltd; the AUCAT-101 catalyst and the CUCAT-U2 catalyst are produced by Guangzhou Youyun chemical materials, Inc.; the antioxidant-264 is commercially available 2, 6-di-tert-butyl-4-methylphenol; the Defom5500 antifoaming agent is produced by moderate chemistry Co., Ltd; the 8-hydroxyquinolinone mildew preventive is a commercial industrial product 8-hydroxyquinolinone; the fiber bundle is 8mm glass fiber; the stones are formed by crushing granite, basalt and limestone natural stones with the diameter of 5-10 mm.

The preparation method of the underwater pier pouring type polyurethane composite material anti-collision fence comprises the following steps:

step one, preparation of a component A:

step 1: step 1: adding 1 part of antioxidant-264 into 3 parts of triisopropanolamine, adding 5 parts of glycerol, further stirring and dissolving, then adding 4 parts of water, and uniformly stirring and dissolving to obtain a mixed solution A1;

step 2: slowly adding the mixed solution A1 into 87 parts of water glass under the condition that the stirring speed is 30r/min, and continuously stirring for 20 minutes to obtain a component A for later use;

step two, preparing the component B:

adding 75 parts of PAPI into a mixing container, adding 15 parts of polyurethane prepolymer into the mixing container, and stirring and mixing uniformly at normal temperature; then sequentially adding 3 parts of dioctyl phthalate, 1 part of AUCAT-101 catalyst, 1 part of CUCAT-U2 catalyst, 1.5 parts of Defom5500 defoaming agent, 2.5 parts of HyMax220 hydrolysis resistant agent and 1 part of 8-hydroxyquinolinone mildew preventive, stirring and mixing uniformly at normal temperature, vacuumizing and defoaming until the mixed liquid is transparent to obtain a component B, filling dry nitrogen, sealing and storing for later use;

thirdly, preparing the underwater pier pouring type polyurethane composite material anti-collision fence:

step 1: enclosing a pier to be protected by using a basalt fiber reinforced plastic sleeve with the thickness of 8mm, wherein the diameter of the sleeve is determined by the specific situation on site, and the joints are connected by nylon threads;

step 2: the water between the basalt fiber reinforced plastic sleeve fence and the pier does not need to be pumped out completely and is put into: 200 parts of stones with the diameter of 5-10 mm, mixing 10 parts of fiber bundles into the stones, placing the stones and the fiber bundles, and pouring 200 parts of mixture of the component A and the component B by using a pneumatic grouting pump for mining produced by Shanxi solidification new materials Co., Ltd, wherein a grouting machine with the model of 2ZBQ-8/10 is used for pouring, and the continuous construction and pouring can be realized; and (3) curing the casting material for 2-3 min, and after further curing is completed for 48 hours, obtaining the underwater pier casting type polyurethane composite material anti-collision fence.

Example 2

According to the underwater pier pouring type polyurethane composite material anti-collision fence, the anti-collision fence is arranged on the outer side of a lower structure of a pier, and the outer layer of the anti-collision fence is a basalt fiber reinforced plastic sleeve which plays a shaping role; a polyurethane composite material buffer layer with a buffering effect is arranged between the basalt fiber reinforced plastic sleeve and the pier, and the fiber reinforced water glass modified polyurethane material is matched with stone for cast-in-place molding;

the basalt fiber reinforced plastic sleeve is a sleeve device made of basalt fiber reinforced unsaturated polyester, epoxy resin, phenolic resin or a plurality of composite resins, the thickness of the sleeve is 9mm, and the diameter of the sleeve is determined by the specific conditions of a site pier.

The polyurethane composite material buffer layer is formed by casting the component A, the component B and the component C in situ by matching with stone materials:

the component A comprises: 89 parts of water glass, 3 parts of glycerol, 3 parts of triisopropanolamine, 4 parts of water and 1 part of antioxidant-264;

the component B comprises: 77 parts of PAPI, 14 parts of polyurethane prepolymer, 2.5 parts of dioctyl phthalate, 1 part of AUCAT-101 catalyst, 0.8 part of CUCAT-U2 catalyst, 1.3 parts of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.9 part of 8-hydroxyquinolinone mildew preventive;

the component C comprises: 13 parts of fiber bundles and 300 parts of stones.

The water glass is sodium silicate water glass, the modulus is 2.2-2.4, and the density is 1.4-1.5 g/cm³(20 ℃) and the baume degree is 48-52 degrees.

The preparation method of the polyurethane prepolymer in the component B comprises the following steps:

accurately weighing 100 parts of polyether polyol N220, dehydrating for 2 hours at 120 ℃ and-0.09 MPa, accurately adding 32.16 parts of MDI-100 diisocyanate when the temperature is reduced to 50 ℃, reacting for 30 minutes at 50 ℃, then heating to 80-82 ℃, reacting for 2.0 hours, vacuumizing and defoaming for 30 minutes until the reactant is colorless transparent liquid, and thus obtaining the polyurethane prepolymer with the-NCO content of 5%.

The PAPI is polyphenyl polymethylene polyisocyanate, and the mass content of-NCO groups is 31.1-31.5%; the MDI-100 is 4, 4' -diphenylmethane diisocyanate, and the mass content of-NCO groups is 33.6%; the polyether polyol N220 is polyether polyol with the average molecular weight of 2000; the HyMax220 hydrolysis resistant agent is sold by Shanghai Langyi functional materials Co.Ltd; the AUCAT-101 catalyst and the CUCAT-U2 catalyst are produced by Guangzhou Youyun chemical materials, Inc.; the antioxidant-264 is commercially available 2, 6-di-tert-butyl-4-methylphenol; the Defom5500 antifoaming agent is produced by moderate chemistry Co., Ltd; the 8-hydroxyquinolinone mildew preventive is a commercial industrial product 8-hydroxyquinolinone; the fiber bundle is formed by doping 9mm glass fiber and basalt fiber; the stones are formed by crushing granite, basalt and limestone natural stones with the diameter of 5-10 mm.

The preparation method of the underwater pier pouring type polyurethane composite material anti-collision fence comprises the following steps:

step one, preparation of a component A:

step 1: adding 1 part of antioxidant-264 into 3 parts of triisopropanolamine, adding 3 parts of glycerol, further stirring and dissolving, then adding 4 parts of water, and uniformly stirring and dissolving to obtain a mixed solution A1;

step 2: slowly adding the mixed solution A1 into 89 parts of water glass under the condition that the stirring speed is 30r/min, and continuously stirring for 20 minutes to obtain a component A;

step two, preparing the component B:

and step 3: adding 77 parts of PAPI into a mixing container, adding 14 parts of polyurethane prepolymer into the mixing container, and stirring and mixing uniformly at normal temperature; then sequentially adding 2.5 parts of dioctyl phthalate, 1 part of AUCAT-101 catalyst, 0.8 part of CUCAT-U2 catalyst, 1.3 parts of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.9 part of 8-hydroxyquinolinone mildew preventive, stirring and mixing uniformly at normal temperature, vacuumizing and defoaming until the mixed liquid is transparent to obtain a component B, filling dry nitrogen, and sealing and storing;

thirdly, preparing the underwater pier pouring type polyurethane composite material anti-collision fence:

step 1: enclosing a pier to be protected by a basalt fiber reinforced plastic sleeve with the thickness of 9mm, wherein the diameter of the sleeve is determined by the specific condition of the diameter of the pier on site, and the joint is connected by a nylon wire;

step 2: the water between the basalt fiber reinforced plastic sleeve fence and the pier does not need to be pumped out completely and is put into: 300 parts of stones with the diameter of 5-10 mm, 13 parts of fiber bundles are mixed into the stones, a mining pneumatic grouting pump produced by Shanxi solidification new materials company Limited is used while the stones and the fiber bundles are placed, and a grouting machine with the model of 2ZBQ-8/10 is used for pouring 200 parts of mixture of the component A and the component B, and the mixture can be intermittently constructed and poured; and (3) curing the casting material for 2-3 min, and after further curing is completed for 48 hours, obtaining the underwater pier casting type polyurethane composite material anti-collision fence.

Example 3

According to the underwater pier pouring type polyurethane composite material anti-collision fence, the anti-collision fence is arranged on the outer side of a lower structure of a pier, and the outer layer of the anti-collision fence is a basalt fiber reinforced plastic sleeve which plays a shaping role; a polyurethane composite material buffer layer with a buffering effect is arranged between the basalt fiber reinforced plastic sleeve and the pier, and the fiber reinforced water glass modified polyurethane material is matched with stone for cast-in-place molding.

The basalt fiber reinforced plastic sleeve is a sleeve device made of basalt fiber reinforced unsaturated polyester, epoxy resin, phenolic resin or a plurality of composite resins, the thickness of the sleeve is 9mm, and the diameter of the sleeve is determined by the specific situation of the diameter of an on-site pier.

The polyurethane composite material buffer layer is formed by casting the component A, the component B and the component C in situ by matching with stone materials:

the component A comprises: 91 parts of water glass, 3 parts of glycerol, 3 parts of triisopropanolamine, 2.5 parts of water and 0.5 part of antioxidant-264;

the component B comprises: 78 parts of PAPI, 13 parts of polyurethane prepolymer, 3 parts of dioctyl phthalate, 0.8 part of AUCAT-101 catalyst, 0.7 part of CUCAT-U2 catalyst, 1.2 parts of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.8 part of 8-hydroxyquinolinone mildew preventive;

the component C comprises: 15 parts of fiber bundles and 400 parts of stones.

The water glass is sodium silicate water glass, the modulus is 2.2-2.4, and the density is 1.4-1.5 g/cm³(20 ℃) and the baume degree is 48-52 degrees.

The preparation method of the polyurethane prepolymer in the component B comprises the following steps:

accurately weighing 100 parts of polyether polyol N220, dehydrating for 2h under the conditions of 120 ℃ and-0.09 MPa, accurately adding 36.96 parts of MDI-100 diisocyanate when the temperature is reduced to 50 ℃, reacting for 30min at 50 ℃, then heating to 80-82 ℃, reacting for 2.0h, vacuumizing and defoaming for 30min until the reactant is colorless transparent liquid, and thus obtaining the polyurethane prepolymer with the-NCO content of 6%.

The PAPI is polyphenyl polymethylene polyisocyanate, and the mass content of-NCO groups is 31.1-31.5%; the MDI-100 is 4, 4' -diphenylmethane diisocyanate, and the mass content of-NCO groups is 33.6%; the polyether polyol N220 is polyether polyol with the average molecular weight of 2000; the HyMax220 hydrolysis resistant agent is sold by Shanghai Langyi functional materials Co.Ltd; the AUCAT-101 catalyst and the CUCAT-U2 catalyst are produced by Guangzhou Youyun chemical materials, Inc.; the antioxidant-264 is commercially available 2, 6-di-tert-butyl-4-methylphenol; the Defom5500 antifoaming agent is produced by moderate chemistry Co., Ltd; the 8-hydroxyquinolinone mildew preventive is a commercial industrial product 8-hydroxyquinolinone; the fiber bundle is 9mm basalt fiber; the stones are formed by crushing granite, basalt and limestone natural stones with the diameter of 5-10 mm.

The preparation method of the underwater pier pouring type polyurethane composite material anti-collision fence comprises the following steps:

step one, preparation of a component A:

step 1: adding 0.5 part of antioxidant-264 into 3 parts of triisopropanolamine, adding 3 parts of glycerol, further stirring and dissolving, then adding 2.5 parts of water, stirring and dissolving uniformly to obtain a mixed solution A1;

step 2: slowly adding the mixed solution A1 into 91 parts of water glass under the condition that the stirring speed is 30r/min, and continuously stirring for 20 minutes to obtain a component A for later use;

step two, preparing the component B:

adding 78 parts of PAPI into a mixing container, adding 13 parts of polyurethane prepolymer into the mixing container, and stirring and mixing uniformly at normal temperature; then sequentially adding 3 parts of dioctyl phthalate, 0.8 part of AUCAT-101 catalyst, 0.7 part of CUCAT-U2 catalyst, 1.2 parts of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.8 part of 8-hydroxyquinolinone mildew preventive, stirring and mixing uniformly at normal temperature, vacuumizing and defoaming until the mixed liquid is transparent to obtain a component B, filling dry nitrogen, sealing and storing for later use;

thirdly, preparing the underwater pier pouring type polyurethane composite material anti-collision fence:

step 1: enclosing a pier to be protected by a basalt fiber reinforced plastic sleeve with the thickness of 9mm, wherein the diameter of the sleeve is determined by the specific situation on site, and the joints are connected by nylon threads;

step 2: the water between the basalt fiber reinforced plastic sleeve fence and the pier does not need to be pumped out completely and is put into: 400 parts of stones with the diameter of 5-10 mm, 15 parts of fiber bundles are mixed into the stones, 200 parts of A, B mixture is poured by a grouting machine while the stones and the fiber bundles are placed, and continuous construction and pouring can be carried out; and (3) curing the casting material for 2-3 min, and after further curing is completed for 48 hours, obtaining the underwater pier casting type polyurethane composite material anti-collision fence.

The grouting machine is a mining pneumatic grouting pump produced by Shanxi solidification force novel material company Limited and has the model number of 2 ZBQ-8/10.

Example 4

According to the underwater pier pouring type polyurethane composite material anti-collision fence, the anti-collision fence is arranged on the outer side of a lower structure of a pier, and the outer layer of the anti-collision fence is a basalt fiber reinforced plastic sleeve which plays a shaping role; a polyurethane composite material buffer layer with a buffering effect is arranged between the basalt fiber reinforced plastic sleeve and the pier, and the fiber reinforced water glass modified polyurethane material is matched with stone for cast-in-place molding.

The basalt fiber reinforced plastic sleeve is a sleeve device made of basalt fiber reinforced unsaturated polyester, epoxy resin, phenolic resin or a plurality of composite resins, the thickness of the sleeve is 10mm, and the diameter of the sleeve is determined by the specific conditions of a pier on site.

The polyurethane composite material buffer layer is formed by casting the component A, the component B and the component C in situ by matching with stone materials:

the component A comprises: 92 parts of water glass, 3 parts of glycerol, 2 parts of triisopropanolamine, 2 parts of water and 1 part of antioxidant-264;

the component B comprises: 80 parts of PAPI, 12 parts of polyurethane prepolymer, 2.5 parts of dioctyl phthalate, 0.6 part of AUCAT-101 catalyst, 0.6 part of CUCAT-U2 catalyst, 1.1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.7 part of 8-hydroxyquinolinone mildew preventive;

the component C comprises: 18 parts of fiber bundles and 500 parts of stones.

The water glass is sodium silicate water glass, the modulus is 2.2-2.4, and the density is 1.4-1.5 g/cm³(20 ℃) and the baume degree is 48-52 degrees.

The preparation method of the polyurethane prepolymer in the component B comprises the following steps:

accurately weighing 100 parts of polyether polyol N220, dehydrating for 2 hours at 120 ℃ and-0.09 MPa, accurately adding 42.11 parts of MDI-100 diisocyanate when the temperature is reduced to 50 ℃, reacting for 30 minutes at 50 ℃, then heating to 80-82 ℃, reacting for 2.0 hours, vacuumizing and defoaming for 30 minutes until the reactant is colorless transparent liquid, and thus obtaining the polyurethane prepolymer with the-NCO content of 7%.

The PAPI is polyphenyl polymethylene polyisocyanate, and the mass content of-NCO groups is 31.1-31.5%; the MDI-100 is 4, 4' -diphenylmethane diisocyanate, and the mass content of-NCO groups is 33.6%; the polyether polyol N220 is polyether polyol with the average molecular weight of 2000; the HyMax220 hydrolysis resistant agent is sold by Shanghai Langyi functional materials Co.Ltd; the AUCAT-101 catalyst and the CUCAT-U2 catalyst are produced by Guangzhou Youyun chemical materials, Inc.; the antioxidant-264 is commercially available 2, 6-di-tert-butyl-4-methylphenol; the Defom5500 antifoaming agent is produced by moderate chemistry Co., Ltd; the 8-hydroxyquinolinone mildew preventive is a commercial industrial product 8-hydroxyquinolinone; the fiber bundle is 10mm glass fiber; the stones are formed by crushing granite, basalt and limestone natural stones with the diameter of 5-10 mm.

The preparation method of the underwater pier pouring type polyurethane composite material anti-collision fence comprises the following steps:

step one, preparation of a component A:

step 1: adding 1 part of antioxidant-264 into 2 parts of triisopropanolamine, adding 3 parts of glycerol, further stirring and dissolving, then adding 2 parts of water, and uniformly stirring and dissolving to obtain a mixed solution A1;

adding 1 part of CUCAT-WN catalyst into 2 parts of water, stirring and dissolving uniformly, adding 3 parts of glycerol and 2 parts of triisopropanolamine, stirring and mixing, and obtaining a mixed solution A1;

step 2: slowly adding the mixed solution A1 into 92 parts of water glass under the condition that the stirring speed is 30r/min, and continuously stirring for 20 minutes to obtain a component A for later use;

step two, preparing the component B:

adding 80 parts of PAPI into a mixing container, adding 12 parts of polyurethane prepolymer into the mixing container, and stirring and mixing uniformly at normal temperature; then sequentially adding 2.5 parts of dioctyl phthalate, 0.6 part of AUCAT-101 catalyst, 0.6 part of CUCAT-U2 catalyst, 1.1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.7 part of 8-hydroxyquinolinone mildew preventive, stirring and mixing uniformly at normal temperature, vacuumizing and defoaming until the mixed liquid is transparent to obtain a component B, filling dry nitrogen, sealing and storing for later use;

thirdly, preparing the underwater pier pouring type polyurethane composite material anti-collision fence:

step 1: enclosing a pier to be protected by a basalt fiber reinforced plastic sleeve with the thickness of 10mm, wherein the diameter of the sleeve is determined by the specific situation on site, and the seam is connected by a nylon wire;

step 2: the water between the basalt fiber reinforced plastic sleeve fence and the pier does not need to be pumped out completely and is put into: 500 parts of stones with the diameter of 5-10 mm, 18 parts of fiber bundles are mixed into the stones, 200 parts of A, B mixture is poured by a grouting machine while the stones and the fiber bundles are placed, and continuous construction and pouring can be carried out; and (3) curing the casting material for 2-3 min, and after further curing is completed for 48 hours, obtaining the underwater pier casting type polyurethane composite material anti-collision fence.

The grouting machine is a mining pneumatic grouting pump produced by Shanxi solidification force novel material company Limited and has the model number of 2 ZBQ-8/10.

Example 5

According to the underwater pier pouring type polyurethane composite material anti-collision fence, the anti-collision fence is arranged on the outer side of a lower structure of a pier, and the outer layer of the anti-collision fence is a basalt fiber reinforced plastic sleeve which plays a shaping role; a polyurethane composite material buffer layer with a buffering effect is arranged between the basalt fiber reinforced plastic sleeve and the pier, and the fiber reinforced water glass modified polyurethane material is matched with stone for cast-in-place molding.

The basalt fiber reinforced plastic sleeve is a sleeve device prepared from basalt fiber reinforced unsaturated polyester, epoxy resin, phenolic resin or a plurality of composite resins, the thickness of the sleeve is 10mm, and the diameter of the sleeve is determined by the specific conditions on site.

The polyurethane composite material buffer layer is formed by casting the component A, the component B and the component C in situ by matching with stone materials:

the component A comprises: 94 parts of water glass, 2 parts of glycerol, 2 parts of triisopropanolamine, 1.5 parts of water and 0.5 part of antioxidant-264;

the component B comprises: 81 parts of PAPI, 12 parts of polyurethane prepolymer, 2 parts of dioctyl phthalate, 0.5 part of AUCAT-101 catalyst, 0.5 part of CUCAT-U2 catalyst, 1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.5 part of 8-hydroxyquinolinone mildew preventive;

the component C comprises: 20 parts of fiber bundles and 600 parts of stones.

The water glass is sodium silicate water glass, the modulus is 2.2-2.4, and the density is 1.4-1.5 g/cm³(20 ℃) and the baume degree is 48-52 degrees.

The preparation method of the polyurethane prepolymer comprises the following steps:

accurately weighing 100 parts of polyether polyol N220, dehydrating for 2 hours at 120 ℃ and-0.09 MPa, accurately adding 42.11 parts of MDI-100 diisocyanate when the temperature is reduced to 50 ℃, reacting for 30 minutes at 50 ℃, then heating to 80-82 ℃, reacting for 2.0 hours, vacuumizing and defoaming for 30 minutes until the reactant is colorless transparent liquid, and thus obtaining the polyurethane prepolymer with the-NCO content of 7%.

The PAPI is polyphenyl polymethylene polyisocyanate, and the mass content of-NCO groups is 31.1-31.5%; the MDI-100 is 4, 4' -diphenylmethane diisocyanate, and the mass content of-NCO groups is 33.6%; the polyether polyol N220 is polyether polyol with the average molecular weight of 2000; the HyMax220 hydrolysis resistant agent is sold by Shanghai Langyi functional materials Co.Ltd; the AUCAT-101 catalyst is produced by Guangzhou Youyun chemical materials Co.Ltd; the antioxidant-264 is commercially available 2, 6-di-tert-butyl-4-methylphenol; the Defom5500 antifoaming agent is produced by moderate chemistry Co., Ltd; the mildew preventive is a commercial industrial product 8-hydroxyquinolinone; the fiber bundle is one of glass fiber or basalt fiber with the diameter of 10mm, or both of the glass fiber and the basalt fiber can be used in a doped mode, and the stones are formed by crushing natural stones such as granite, basalt and limestone with the diameter of 5-10 mm.

The preparation method of the underwater pier pouring type polyurethane composite material anti-collision fence comprises the following steps:

step one, preparation of a component A:

step 1: adding 0.5 part of antioxidant-264 into 2 parts of triisopropanolamine, adding 2 parts of glycerol, further stirring and dissolving, then adding 1.5 parts of water, stirring and dissolving uniformly to obtain a mixed solution A1;

adding 0.5 part of CUCAT-WN catalyst into 1.5 parts of water, stirring and dissolving uniformly, adding 2 parts of glycerol and 2 parts of triisopropanolamine, stirring and mixing to obtain a mixed solution A1;

step 2: slowly adding the mixed solution A1 into 94 parts of water glass under the condition that the stirring speed is 30r/min, and continuously stirring for 20 minutes to obtain a component A for later use;

step two, preparing the component B:

and step 3: adding 81 parts of PAPI into a mixing container, adding 12 parts of polyurethane prepolymer into the mixing container, and stirring and mixing uniformly at normal temperature; then sequentially adding 2 parts of dioctyl phthalate, 0.5 part of AUCAT-101 catalyst, 0.5 part of CUCAT-U2 catalyst, 1 part of Defom5500 defoamer, 2.5 parts of HyMax220 hydrolysis resistant agent and 0.5 part of 8-hydroxyquinolinone mildew preventive, stirring and mixing uniformly at normal temperature, vacuumizing and defoaming until the mixed liquid is transparent to obtain a component B, filling dry nitrogen, sealing and storing for later use;

thirdly, preparing the underwater pier pouring type polyurethane composite material anti-collision fence:

step 1: enclosing a pier to be protected by a basalt fiber reinforced plastic sleeve with the thickness of 10mm, wherein the diameter of the sleeve is determined by the specific situation on site, and the seam is connected by a nylon wire;

step 2: the water between the basalt fiber reinforced plastic sleeve fence and the pier does not need to be completely pumped out and put in: 600 parts of stones with the diameter of 5-10 mm, mixing 20 parts of fiber bundles into the stones, placing the stones and the fiber bundles, and pouring 200 parts of A, B mixture by using a grouting machine, wherein continuous construction and pouring can be realized; and (3) curing the casting material for 2-3 min, and after further curing is completed for 48 hours, obtaining the underwater pier casting type polyurethane composite material anti-collision fence.

The grouting machine is a mining pneumatic grouting pump produced by Shanxi solidification force novel material company Limited and has the model number of 2 ZBQ-8/10.

With reference to related national standards of GB/T2567-2008 & lt resin casting body performance test method & gt, GB/T529-2008 & lt vulcanized rubber or thermoplastic rubber tear strength measurement & gt GB/T1040.2-2006 & lt plastic tensile property test method & gt and the like, the mechanical properties of the liquid material of the underwater pier anti-collision polyurethane fence are measured and shown in Table 1.

TABLE 1 pier pouring type polyurethane composite material anti-collision fence performance in water

Name (R)	Soaking in water for 30 days after molding	Standing in the atmosphere for 30 days after molding
			Shore D hardness	62	64
Tensile strength/MPa ≥	18	17
			Tear Strength/KN m-1，≥	25	25
Compressive strength/MPa ≥	61	62
			Bending strength/MPa ≥	21	20
Impact Strength/(KJ/m)2)，≥	5	5
			The bonding strength/MPa is not less than	7	7