CN116003023A - A kind of modified glass fiber powder reinforced polyurethane concrete and its preparation method - Google Patents

Abstract

The invention discloses modified glass fiber powder reinforced polyurethane concrete, and belongs to the technical field of polyurethane concrete. The raw material components of the polyurethane adhesive comprise polyurethane adhesive and aggregate, wherein the polyurethane adhesive comprises 5-20wt% of siloxane coupling agent modified glass fiber powder; the preparation method of the siloxane coupling agent modified glass fiber powder comprises the following steps: dissolving a siloxane coupling agent in a water/ethanol mixed solution, and uniformly stirring; grinding glass fiber, sieving with 1000 mesh sieve to obtain glass fiber powder, adding into solution, and performing ultrasonic treatment; and (5) after ultrasonic treatment, washing with ethanol and drying to obtain the product. The addition of 15wt% glass fiber powder composite produced a polymer that enhanced the static elastic modulus by 38.7%, flexural strength by 112.0%, flexural modulus by 225.3% and adhesive strength by 44.9% relative to pure polyurethane concrete.

Description

A kind of modified glass fiber powder reinforced polyurethane concrete and its preparation method

technical field

The invention relates to the technical field of polyurethane concrete, in particular to a modified glass fiber powder reinforced polyurethane concrete and a preparation method thereof.

Background technique

Polyurethane concrete is a pavement repair material formed by physically mixing polyurethane adhesives instead of cement-based materials as cementitious materials and inorganic aggregates. Because of its fast curing time and strong bonding ability, it has attracted a lot of attention from both industry and academia. Compared with ordinary cement, polymer concrete has unique properties, including strong chemical resistance, high specific strength, short curing time, strong bonding ability, and excellent sound insulation performance.

Compared with other resins, polyurethane adhesives have better toughness, faster curing rate, excellent low temperature elasticity, low cost and can be prepared without solvents. Polyurethanes are mainly used as repair materials or decorative materials, but they are also recently used in some fields as the main body of building materials. Polyurethane polymer concrete has high compressive strength, high flexural strength and also cures quickly. Polyurethane concrete has excellent chemical resistance, weather resistance, abrasion resistance, and is less prone to cracks and damage. Ordinary cement concrete is very easy to generate voids and cracks, and causes the generation of secondary cracks. The movement of the corroded substrate through cracks and voids causes the concrete to crumble and ultimately lead to failure of the overall structure. In polyurethane polymer concrete, the polymer can fill the voids between the aggregates, thereby reducing the probability of external corrosion attacking the concrete.

However, when the polyurethane adhesive, which is a fast-curing adhesive at room temperature, is used in polymer concrete, its static elastic modulus and flexural modulus are relatively weak, and it is easy to deform, which limits its application range and is also prone to cracking.

Contents of the invention

The technical problem to be solved in the present invention is to overcome the deficiencies of the prior art, to provide a modified glass fiber powder reinforced polyurethane concrete and its preparation method, and the polyurethane concrete prepared by using modified glass fiber powder has a higher modulus of elasticity and flexural modulus.

In order to solve the above technical problems, the present invention adopts the following technical solutions.

A modified glass fiber powder reinforced polyurethane concrete, its raw material components include polyurethane adhesive and aggregate, the polyurethane adhesive includes 5-20wt% siloxane coupling agent modified glass fiber powder; The aggregate is the Chinese standard sand that meets the industrial standard (JC/T108-2008);

The preparation method of described siloxane coupling agent modified glass fiber powder is as follows:

Dissolve the siloxane coupling agent in the water/ethanol mixed solution and stir evenly; grind the glass fiber through a 1000-mesh sieve to obtain glass fiber powder, add it to the solution, and perform ultrasonic treatment; after ultrasonic cleaning, wash with ethanol and dry to obtain the product.

Specifically, glass fiber powder uses a grinder to grind waste glass fiber powder into powder, and the powder is passed through a 1000-mesh sieve. The functional groups on the surface of the modified particles are treated with a siloxane coupling agent. First, the oxane coupling agent was dissolved in a water/ethanol mixed solvent and stirred for 1 hour. Next, glass fiber powder was added into the solution, and the above mixture was sonicated for 1 hour with a cell pulverizer. After ultrasonication, the glass fiber powder was washed twice with ethanol to remove the remaining siloxane, and finally dried in an oven at 120 °C for 2 hours.

Preferably, the amount of the siloxane coupling agent is 1.9-2.1 wt% of the mass of the water/ethanol mixed solution.

Preferably, the mass ratio of water and ethanol in the water/ethanol mixed solution is 1:1-1.2.

Preferably, the mass ratio of glass fiber powder to siloxane coupling agent is 50-55:1.

Preferably, the siloxane coupling agent is aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane A type of silane.

Preferably, by weight percentage, the adhesive further includes: 4,4'-methylene-bis(o-chloroaniline) 15-20 wt%, polyoxypropylene ether glycol 65-70 wt%, catalyst 0.1- 0.3wt%, defoamer 0.25-0.75wt%, polymethylene polyisocyanate 10-15wt%.

Preferably, the Mn of the polyoxypropylene ether glycol is 2000 g/mol.

聚亚甲基多异氰酸酯为多苯基多亚甲基多异氰酸酯。Preferably, the catalyst is bismuth isooctanoate (Bi(Oc) ₂ ), and the defoamer is

Polymethylene polyisocyanates are polyphenyl polymethylene polyisocyanates.

Preferably, the preparation method of described adhesive comprises the steps:

Mix 4,4'-methylene-bis(o-chloroaniline), polyoxypropylene ether glycol, catalyst, and defoamer, and stir for 0.8-1.2 hours in a flask at 80°C under a nitrogen atmosphere; the mixture is cooled and stored sealed Put it in a container for use; add siloxane modified glass fiber powder, stir evenly; then mix evenly with polymethylene polyisocyanate; pour into a mold, and maintain at room temperature to obtain a polyurethane adhesive.

Preferably, in parts by weight, it includes: 25-35 parts of polyurethane adhesive, and 65-75 parts of aggregate.

A kind of preparation method of above-mentioned modified glass fiber powder reinforced polyurethane concrete, comprises the steps:

Mix the polyurethane adhesive and aggregate evenly, pour it into the mold, and maintain it after demoulding.

The invention adopts siloxane coupling agent to treat and modify the functional groups on the surface of the glass fiber particles to increase the wettability of the glass fiber powder. The glass fiber powder is ground through a 1000-mesh sieve and has a large specific surface area, and the siloxane coupling agent has little effect on the size distribution of the glass fiber powder particles. The strong hydrogen bond interaction between the modified glass fiber powder restricts the movement of the polyurethane chain segment, thereby increasing the rigidity of the chain segment. The presence of modified glass fiber powder can effectively limit the formation of cracks between aggregate and polyurethane, thereby improving the mechanical properties of polyurethane adhesives. The addition of modified glass fiber powder can effectively improve the thermal stability of polyurethane adhesives. The crystallinity of polyurethane decreases as the content of modified glass fiber powder increases, and the strong hydrogen bond interaction between polymer and inorganic particles also limits the crystallization of polyurethane hard segments. The soft segment of polyurethane is composed of polyoxypropylene ether glycol chains, which have long intertwined chains; the hard segment of polyurethane is composed of polyphenylpolymethylene polyisocyanate and 4,4'-methylene-bis(o-chloro Aniline), the hard segment is dispersed in the soft segment as the continuous phase as the dispersed phase.

Compared with the prior art, the present invention has the advantages of:

The modified glass fiber powder reinforced polyurethane concrete provided by the invention improves the mechanical properties of the concrete and enhances the thermal stability by modifying the glass fibers. Compared with cement concrete, polyurethane concrete has a lower static elastic modulus and higher elastic deformation capacity. The strong interfacial bonding ability between the polyurethane substrate and the modified glass fiber powder particles limits the chain segment movement of the polyurethane substrate. Compared with pure polyurethane concrete, the polymer prepared by adding 15wt% glass fiber powder compound enhanced the static elastic modulus by 38.7%, the flexural strength by 112.0%, the flexural modulus by 225.3% and the bond strength by 44.9%.

Description of drawings

Fig. 1 is the compressive stress-strain curve of polyurethane concrete after curing;

Fig. 2 is the variation curve of compressive strength and static modulus of elasticity of polyurethane concrete with glass fiber content;

Fig. 3 is the flexural stress-strain curve of the polyurethane concrete after curing;

Fig. 4 is the variation curve of flexural strength and flexural modulus of polyurethane concrete with glass fiber content.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby. In the following examples, unless otherwise specified, the raw materials and instruments used are all commercially available.

Raw material and equipment used in the embodiment are as follows:

Aminopropyltriethoxysilane: analytically pure, Chenguang.

4,4'-methylene-bis(o-chloroaniline): analytically pure, Suzhou Xiangyuan Chemical Co., Ltd.

Polyoxypropylene ether diol: Mn=2000g/mol, Shandong Bluestar Dongda Chemical Co., Ltd.

Bismuth isooctanoate (Bi(Oc) ₂ : analytically pure, Shanghai Deyin Chemical Co., Ltd.

分析纯，德国默克公司。

Analytical pure, Merck, Germany.

Polyphenyl polymethylene polyisocyanate: analytically pure, Wanhua Chemical Group Co., Ltd.

Water: tap water.

Embodiment 1 (comparative example)

Dissolve 2g of aminopropyltriethoxysilane in 100g of water/ethanol (1:1 mass ratio), and stir for 1 hour. Next, glass fiber powder particles were added into the solution, and the above mixture was sonicated for 1 hour with a cell pulverizer. After ultrasonication, the glass fiber powder particles were washed twice with ethanol to remove the remaining siloxane, and finally dried in an oven at 120 °C for 2 hours.

上述物质混合，在烧瓶内80℃氮气氛围下搅拌1小时。混合物冷却后贮存密封在容器内待用。Prepare the polymer adhesive Base component of polymer concrete: 53.4g 4,4'-methylene-bis(o-chloroaniline), 200g polyoxypropylene ether glycol, 0.5g bismuth isooctanoate (Bi(Oc ) ₂ ), 1.25g

The above materials were mixed and stirred for 1 hour in a flask at 80° C. under a nitrogen atmosphere. Store the mixture in sealed containers after cooling.

The Base component of the polyurethane adhesive was vigorously stirred with a mechanical stirring paddle for 5 minutes. The mixture and 40 g of polyphenyl polymethylene polyisocyanate were mixed in a disposable cup for 2 minutes to obtain a polyurethane adhesive.

Example 2

Dissolve 2g of aminopropyltriethoxysilane in 100g of water/ethanol (1:1 mass ratio), and stir for 1 hour. Next, glass fiber powder particles were added into the solution, and the above mixture was sonicated for 1 hour with a cell pulverizer. After ultrasonication, the glass fiber powder particles were washed twice with ethanol to remove the remaining siloxane, and finally dried in an oven at 120 °C for 2 hours.

上述物质混合，在烧瓶内80℃氮气氛围下搅拌1小时。混合物冷却后贮存密封在容器内待用。Prepare the polymer adhesive Base component of polymer concrete: 53.4g 4,4'-methylene-bis(o-chloroaniline), 200g polyoxypropylene ether glycol, 0.5g bismuth isooctanoate (Bi(Oc ) ₂ ), 1.25g

The above materials were mixed and stirred for 1 hour in a flask at 80° C. under a nitrogen atmosphere. Store the mixture in sealed containers after cooling.

Add 5 wt% of surface-modified glass fiber powder to the Base component of the polyurethane adhesive. The mixture components were stirred vigorously with a mechanical paddle for 5 minutes. The mixture was then mixed with 40 g of polyphenylpolymethylene polyisocyanate in a disposable cup for 2 minutes. Immediately afterwards, the newly prepared polyurethane/glass fiber powder composite was injected into the mold, and cured at room temperature for 5 hours to obtain the polyurethane adhesive.

Example 3

Dissolve 1.9g of aminopropyltriethoxysilane in 100g of water/ethanol (1:1 mass ratio), and stir for 1 hour. Next, glass fiber powder particles were added into the solution, and the above mixture was sonicated for 1 hour with a cell pulverizer. After ultrasonication, the glass fiber powder particles were washed twice with ethanol to remove the remaining siloxane, and finally dried in an oven at 120 °C for 2 hours.

上述物质混合，在烧瓶内80℃氮气氛围下搅拌1小时。混合物冷却后贮存密封在容器内待用。Prepare the polymer adhesive Base component of polymer concrete: 53.8g 4,4'-methylene-bis(o-chloroaniline), 203g polyoxypropylene ether glycol, 0.5g bismuth isooctanoate (Bi(Oc ) ₂ ), 1.23g

The above materials were mixed and stirred for 1 hour in a flask at 80° C. under a nitrogen atmosphere. Store the mixture in sealed containers after cooling.

15 wt% of surface-modified glass fiber powder was added to the Base component of the polyurethane adhesive. The mixture components were stirred vigorously with a mechanical paddle for 5 minutes. The mixture was then mixed with 40 g of polyphenylpolymethylene polyisocyanate in a disposable cup for 2 minutes. Immediately afterwards, the newly prepared polyurethane/glass fiber powder composite was injected into the mold, and cured at room temperature for 5 hours to obtain the polyurethane adhesive.

Example 4

Dissolve 2.1g of aminopropyltriethoxysilane in 100g of water/ethanol (1:1 mass ratio), and stir for 1 hour. Next, glass fiber powder particles were added into the solution, and the above mixture was sonicated for 1 hour with a cell pulverizer. After ultrasonication, the glass fiber powder particles were washed twice with ethanol to remove the remaining siloxane, and finally dried in an oven at 120 °C for 2 hours.

上述物质混合，在烧瓶内80℃氮气氛围下搅拌1小时。混合物冷却后贮存密封在容器内待用。Prepare the polymer adhesive Base component of polymer concrete: 53.2g 4,4'-methylene-bis(o-chloroaniline), 198g polyoxypropylene ether glycol, 0.5g bismuth isooctanoate (Bi(Oc ) ₂ ), 1.22g

The above materials were mixed and stirred for 1 hour in a flask at 80° C. under a nitrogen atmosphere. Store the mixture in sealed containers after cooling.

Add 20wt% of surface-modified glass fiber powder to the Base component of the polyurethane adhesive. The mixture components were stirred vigorously with a mechanical paddle for 5 minutes. The mixture was then mixed with 40 g of polyphenylpolymethylene polyisocyanate in a disposable cup for 2 minutes. Immediately afterwards, the newly prepared polyurethane/glass fiber powder composite was injected into the mold, and cured at room temperature for 5 hours to obtain the polyurethane adhesive.

Embodiment 5 (comparative example)

With 30 parts of polyurethane adhesives in the above-mentioned embodiment 1, 70 parts of aggregates were mixed and stirred in a container for 2 minutes. Finally, the freshly prepared polyurethane concrete is poured into steel molds and compacted with a vibrator. The polyurethane concrete was demoulded after 1 hour and allowed to cure for 4 hours at room temperature.

Example 6

With 30 parts of polyurethane adhesives in the above-mentioned embodiment 1, 70 parts of aggregates were mixed and stirred in a container for 2 minutes. Finally, the freshly prepared polyurethane concrete is poured into steel molds and compacted with a vibrator. The polyurethane concrete was demoulded after 1 hour and allowed to cure for 4 hours at room temperature.

Example 7

30 parts of the polyurethane adhesive in the above-mentioned embodiment 2 and 70 parts of aggregate were mixed and stirred in a container for 2 minutes. Finally, the freshly prepared polyurethane concrete is poured into steel molds and compacted with a vibrator. The polyurethane concrete was demoulded after 1 hour and allowed to cure for 4 hours at room temperature.

Example 8

30 parts of polyurethane adhesive in the above-mentioned embodiment 4, 70 parts of aggregate, and modified glass fiber powder particles were mixed together, and mixed and stirred in a container for 2 minutes. Finally, the freshly prepared polyurethane concrete is poured into steel molds and compacted with a vibrator. The polyurethane concrete was demoulded after 1 hour and allowed to cure for 4 hours at room temperature.

The compressive strength and static modulus of elasticity of the samples of polyurethane concrete in accompanying drawings 1 and 2 are tested; each group of polyurethane concrete samples has three, and each sample is a cube with a size of 20mm×20mm×60mm. A universal tensile machine (SFMIT, WDW-2H) with a 20-ton load capacity was used to test the compressive stress-strain curves of polyurethane concrete at room temperature. The compression test conforms to the ASTM 579-01 standard, and the sample is tested at room temperature at a crosshead rate of 40MPa/min. The sample is 20mm x 20mm placed face up and tested until crushed. Record the compressive stress-response curve to obtain the compressive strength and static modulus of elasticity.

The behavior of polyurethane concrete in Figure 1 is similar to that of elastomers. Compared with cement concrete, polyurethane concrete has a lower static elastic modulus and higher elastic deformation capacity. Referring to the previous literature on polyurethane concrete, the compressive stress-strain curves of this experiment are divided into three deformation stages before reaching the maximum compressive strain. The first stage is the strain interval between 0-1%, and has the smallest slope. This stage is mainly related to the compaction of the polyurethane substrate. The second deformation stage is located at strain 1-4%, with a larger slope. This is due to the improved pressure resistance of the polyurethane substrate after it has been compacted in the first stage. The third stage is at 4-20%, which is due to the fracture of the interface between the polyurethane substrate and the modified glass fiber particles, therefore, the slope gradually decreases until the compressive stress reaches the maximum value.

Figure 2 shows the compressive properties of polyurethane concrete containing different mass fractions of modified glass fiber particles, including compressive strength and static modulus of elasticity. The results show that adding modified glass fiber particles to polyurethane concrete can effectively improve the static elastic modulus of the material. When the content of modified glass fiber particles is between 0-15wt%, the static elastic modulus of polyurethane concrete increases with the increase of modified glass fiber particle content, when the modified glass fiber particle content exceeds 15wt%, the static elastic modulus Volume down. The largest static elastic modulus is the polymer concrete prepared with 10wt% modified glass fiber particles, the static elastic modulus is 216.11±13.16MPa, which is 39.5% higher than the strength of pure polyurethane concrete 154.97±11.62MPa. The reinforcing effect of the modified glass fiber particles was attributed to the strong interfacial bonding ability between the polyurethane substrate and the modified glass fiber particles, which restricted the segmental motion of the polyurethane substrate. When the content of modified glass fiber particles exceeds 20wt%, the static modulus of elasticity decreases significantly, because the aggregation of fillers introduces stress concentration and leads to performance degradation.

Flexural strength and flexural modulus tests of polyurethane concrete samples in Figures 3 and 4: According to the ISO 178:2010 standard, a three-point flexural test was performed on a prismatic spline with a size of 10mm×20mm×200mm. The splines are placed symmetrically on two supports with a span of 160mm. At room temperature, the flexural stress-strain curve was recorded at a displacement rate of 0.07mm/s.

Accompanying drawing 3 is the compressive curve of the polymer concrete of the adhesive of polymer concrete. Accompanying drawing 4 is the flexural strength and the static modulus of elasticity of the polymer concrete of the polymer concrete adhesive. The compressive strength and flexural strength of the polyurethane concrete of the comparative example are 8.06±0.61MPa and 299.66±38.84MPa, respectively. Obviously, the flexural strength and flexural modulus increase significantly with the increase of modified glass fiber particle content, and when the modified glass fiber particle content reaches 15wt%, the flexural strength and flexural modulus of polyurethane concrete reach the maximum value. Compared with the corresponding parameters of pure polyurethane concrete, they are 112.0% and 225.3% higher respectively. When the content of the modified glass fiber particles reaches 20wt%, the modified glass fiber particles begin to agglomerate, causing stress concentration, which leads to a decrease in the flexural strength and flexural modulus. It is worth noting that the enhanced effect of modified glass fiber particles on the flexural strength is significantly greater than that on the compressive strength. This indicates that the magnitude of the flexural strength is greatly influenced by the interaction force between the particles and the organic substrate. Although the compressive strength of polyurethane concrete is lower than that of cement concrete, the flexural strength of polyurethane concrete is significantly higher than that of cement concrete.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with the art, without departing from the spirit and technical solutions of the present invention, can use the methods and technical content disclosed above to make many possible changes and modifications to the technical solutions of the present invention, or modify them to be equivalent Variations of equivalent embodiments. Therefore, any simple modifications, equivalent replacements, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention, which do not deviate from the technical solutions of the present invention, still fall within the protection scope of the technical solutions of the present invention.

Claims (10)

1. a modified glass fiber powder reinforced polyurethane concrete, its raw material components include polyurethane adhesive and aggregate, it is characterized in that, described adhesive comprises 5-20wt% siloxane coupling agent modified glass fiber powder; The preparation method of described siloxane coupling agent modified glass fiber powder is as follows: Dissolve the siloxane coupling agent in the water/ethanol mixed solution and stir evenly; grind the glass fiber through a 1000-mesh sieve to obtain glass fiber powder, add it to the solution, and perform ultrasonic treatment; after ultrasonic cleaning, wash with ethanol and dry to obtain the product. 2. A modified glass fiber powder reinforced polyurethane concrete according to claim 1, characterized in that the amount of the siloxane coupling agent is 1.9 to 2.1 wt% of the mass of the water/ethanol mixed solution. 3. A modified glass fiber powder reinforced polyurethane concrete according to claim 1, characterized in that the mass ratio of water and ethanol in the water/ethanol mixed solution is 1:1 to 1.2. 4. A modified glass fiber powder reinforced polyurethane concrete according to claim 1, characterized in that the mass ratio of glass fiber powder to siloxane coupling agent is 50 to 55:1. 5. A kind of modified glass fiber powder reinforced polyurethane concrete according to claim 1, characterized in that the siloxane coupling agent is aminopropyltriethoxysilane, γ-(2,3-epoxy One of propoxy)propyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. 6. A kind of modified glass fiber powder reinforced polyurethane concrete according to claim 1, characterized in that, by weight percentage, the adhesive also includes: 4,4'-methylene-bis(o- Chloroaniline) 15-20 wt%, polyoxypropylene ether glycol 65-70 wt%, catalyst 0.1-0.3 wt%, defoamer 0.25-0.75 wt%, polymethylene polyisocyanate 10-15 wt%. 7. a kind of modified glass fiber powder reinforced polyurethane concrete according to claim 6, is characterized in that, described catalyzer is bismuth isooctanoate, defoamer is

-6019; the polymethylene polyisocyanate is at least one of polymethylene polyaryl isocyanate, polyphenylpolymethyl polyisocyanate, polymethylene polyphenyl polyisocyanate, wherein NCO functionality It is 2.5～3, and the content of NCO measured by the toluene-di-n-butylamine titration method is 30%～40%. 8. a kind of modified glass fiber powder reinforced polyurethane concrete according to claim 6 or 7, is characterized in that, the preparation method of described adhesive comprises the steps: Mix 4,4'-methylene-bis(o-chloroaniline), polyoxypropylene ether glycol, catalyst, and defoamer, and stir for 0.8-1.2 hours in a flask at 80°C under a nitrogen atmosphere; the mixture is cooled and stored sealed Put it in a container for use; add siloxane modified glass fiber powder, stir evenly; then mix evenly with polymethylene polyisocyanate; pour into a mold, and maintain at room temperature to obtain a polyurethane adhesive. 9. A modified glass fiber powder reinforced polyurethane concrete according to any one of claims 1-8, characterized in that, in parts by weight, it comprises: 25-35 parts of polyurethane adhesive, 65-75 parts aggregate. 10. the preparation method of a kind of modified glass fiber powder reinforced polyurethane concrete as claimed in claim 9, is characterized in that, comprises the steps: Mix the polyurethane adhesive and aggregate evenly, pour it into the mold, and maintain it after demoulding.

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