A high-strength flame-retardant vinyl-type rebar adhesive

Abstract

The present invention provides a high-strength flame-retardant vinyl-type rebar-anchoring adhesive, which includes a component A and a component B. The component A includes a vinyl ester unsaturated polyester resin, a bisphenol A-type unsaturated polyester resin, a dicyclopentadiene-type unsaturated polyester resin, a reactive diluent, a filler I, and a penetrant. The penetrant includes, by mass, 20-40 parts of an acidic polymer alkylammonium salt solution, 35-60 parts of a salt solution of a long-chain polyamine amide and a polar acidic ester, and 15-35 parts of a polyether-modified polydimethylsiloxane. The present invention reduces the interfacial tension between the adhesive and the substrate by adding a specific penetrant to the flame-retardant rebar-anchoring adhesive, so that the adhesive can quickly and fully spread on the surface of the substrate and wet and penetrate, the infiltration and penetration efficiency is improved, the colloidal base material can fully fill the gap, the bonding area between the adhesive and the stone is increased, and the bonding strength between the rebar-anchoring adhesive and the substrate is greatly improved.

Description

Technical Field

[0001] The invention relates to the technical field of building materials, in particular to a high-strength flame-retardant vinyl-type rebar-anchoring adhesive. Background Art

[0002] As an engineering adhesive, anchor glue is widely used in the construction field. Its excellent flame retardancy and mechanical properties are particularly important. In addition, with the rapid development of today's society, people are also pursuing higher work efficiency.

[0003] Existing rebar glues are mainly divided into two categories: one is organic rebar glue based on epoxy resin or vinyl ester resin, and the other is new inorganic rebar glue. Although inorganic rebar glue has a certain degree of flame retardancy, it cannot form a dense protective layer on the outer layer of steel building materials, and its corrosion resistance is relatively poor. As time goes by, the durability of the steel bars will weaken, and there are certain safety hazards. Organic rebar glue can form a good anti-corrosion barrier on the outer layer of steel building materials, but its flame retardant effect is poor. For this reason, researchers have conducted research on organic flame retardant rebar glue. Rebar glue based on epoxy resin has high strength but is expensive, and has a long curing time and low construction efficiency. Rebar glue based on vinyl resin has lower cost and cures quickly. In recent years, researchers have also proposed corresponding improvement plans for its flame retardant properties. For example, the flame retardant vinyl type rebar glue disclosed in Chinese patent document CN105441004A achieves flame retardant effect by adding chlorine-containing and phosphorus-containing active diluents.

[0004] However, like most existing anchoring glue products, the anchoring glue disclosed in CN105441004A has average strength and can no longer meet the current strength requirements of anchoring glue. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention provides a high-strength flame-retardant vinyl-type rebar anchoring adhesive.

[0006] The invention provides a vinyl-type rebar planting adhesive, comprising a component A and a component B. The component A comprises a vinyl ester unsaturated polyester resin, a bisphenol A type unsaturated polyester resin, a dicyclopentadiene type unsaturated polyester resin, a reactive diluent, a filler I and a penetrant. The penetrant comprises, by mass, 20-40 parts of an acidic polymer alkyl ammonium salt solution, 35-60 parts of a salt solution of a long-chain polyamine amide and a polar acidic ester, and 15-35 parts of a polyether-modified polydimethylsiloxane.

[0007] By adding a specific penetrant to the flame-retardant anchoring adhesive, this invention reduces the interfacial tension between the adhesive and the substrate, allowing the adhesive to quickly and fully spread across the substrate surface and penetrate it. Furthermore, the substrate itself has numerous small gaps. As the solid / liquid interfacial tension decreases, the diffusion pressure increases, and the infiltration efficiency improves. The colloidal base material can fully fill these gaps, increasing the bonding area between the adhesive and the stone, significantly enhancing the bonding strength between the adhesive and the substrate.

[0008] According to the vinyl anchoring adhesive provided by the present invention, the mass of the penetrant accounts for 3-11% of the total mass of the unsaturated polyester resin.

[0009] According to the vinyl anchoring glue provided by the present invention, the active diluent is a mixture of a chlorine-containing active diluent and a phosphorus-containing active diluent, wherein the mass ratio of the chlorine-containing active diluent to the phosphorus-containing active diluent is between 1:4 and 4:1.

[0010] The above technical solution can achieve good flame retardant effect by adding chlorine-containing and phosphorus-containing active diluents, and the flame retardant oxygen index is 37-42%.

[0011] According to the vinyl anchoring adhesive provided by the present invention, the chlorine-containing active diluent is 2,5-dichlorostyrene and / or 2,6-dichlorostyrene.

[0012] According to the vinyl-type rebar-anchoring adhesive provided by the present invention, the phosphorus-containing reactive diluent is one or more of triallyl phosphate, phenyl diallyl phosphate, octyl diallyl phosphate and cresyl diallyl phosphate.

[0013] According to the vinyl-type anchoring glue provided by the present invention, the A component includes, by weight: 60-85 parts of vinyl ester unsaturated polyester resin, 10-25 parts of bisphenol A unsaturated polyester resin, 5-15 parts of dicyclopentadiene unsaturated polyester resin, 25-35 parts of active diluent, 100-300 parts of filler I and 3-12 parts of penetrant.

[0014] According to the vinyl-type anchoring glue provided by the present invention, the filler I includes, by weight, 10-20 parts of 60-mesh quartz sand, 30-40 parts of 100-mesh quartz sand, 15-25 parts of 200-mesh silicon dioxide, 10-20 parts of 400-mesh heavy calcium carbonate, 5-10 parts of 800-mesh aluminum hydroxide and 5-10 parts of 1250-mesh talc.

[0015] According to the vinyl anchoring adhesive provided by the present invention, the component A further comprises: 0.015-0.08 parts of a polymerization inhibitor, 0.15-0.8 parts of a accelerator, and 3-8 parts of an anti-settling agent.

[0016] According to the vinyl anchoring adhesive provided by the present invention, the polymerization inhibitor is selected from the group consisting of hydroquinone, 2,5-di-tert-butylhydroquinone, methylhydroquinone, p-benzoquinone, and 4-tert-butylcatechol.

[0017] According to the vinyl-type rebar anchoring adhesive provided by the present invention, the accelerator is selected from the group consisting of N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N-methyl-N-hydroxyethylaniline, N-methyl-N-hydroxyethyl-p-toluidine, N,N-dihydroxyethylaniline and its homologues.

[0018] According to the vinyl anchoring adhesive provided by the present invention, the anti-settling agent is composed of 70-90 parts by weight of precipitated silica and 10-30 parts by weight of calcium stearate.

[0019] In a preferred embodiment of the present invention, the A component comprises, by weight: 60-75 parts of vinyl ester unsaturated polyester resin, 15-25 parts of bisphenol A type unsaturated polyester resin, 10-15 parts of dicyclopentadiene type unsaturated polyester resin, 25-35 parts of reactive diluent, 5-12 parts of penetrant, 0.03-0.06 parts of polymerization inhibitor, 0.3-0.6 parts of accelerator, 5-8 parts of anti-settling agent and 150-250 parts of filler I.

[0020] According to the vinyl anchoring adhesive provided by the present invention, the component B includes a curing agent, and the curing agent is a composition of diacyl peroxide and hydroperoxide.

[0021] The present invention selects two curing agents for compounding. Diacyl peroxide first decomposes to generate free radicals to initiate a cross-linking reaction of the resin, which gradually begins to release heat and finally reaches the critical temperature of the hydroperoxide, causing it to start to decompose and initiate polymerization. The hydroperoxide has a higher exothermic temperature and the exothermic polymerization is more gentle and stable. Under the synergistic effect of the two, the resin can react quickly and fully, thereby improving the conversion rate of the resin base material and greatly shortening the curing time and construction period from the original 7 days to 1 day. At the same time, the flexural strength and compressive strength of the adhesive are improved. After 1 day, the flexural strength is tested to be enhanced from the original 28.9 kN to a maximum of 67.3 kN, and the compressive strength is enhanced from the original 38.4 kN to a maximum of 93.3 kN. After 7 days, the flexural strength is tested to be enhanced from the original 54.7 kN to a maximum of 67.8 kN, and the compressive strength is enhanced from the original 74.5 kN to a maximum of 93.5 kN.

[0022] According to the vinyl-type rebar anchoring glue provided by the present invention, the diacyl peroxide is selected from one or more of benzoyl peroxide and dilauroyl peroxide; the hydroperoxide is selected from one or more of cumene hydroperoxide and tert-butyl hydroperoxide; the mass ratio of the diacyl peroxide to the hydroperoxide is between 1:2 and 2:1.

[0023] According to the vinyl anchoring adhesive provided by the present invention, the component B comprises, in parts by weight: 5-15 parts of a curing agent, 35-50 parts of a conditioning agent and 35-60 parts of a filler II.

[0024] According to the vinyl anchoring adhesive provided by the present invention, the conditioning agent is one or both of dibutyl phthalate and dioctyl phthalate.

[0025] According to the vinyl anchoring adhesive provided by the present invention, the filler II comprises, by weight, 30-50 parts of 400-mesh heavy calcium carbonate, 30-50 parts of 800-mesh aluminum hydroxide and 10-20 parts of 1250-mesh talc.

[0026] In a preferred embodiment of the present invention, the component B comprises, by weight, 7-14 parts of a curing agent, 35-45 parts of a conditioning agent, and 40-55 parts of a filler II.

[0027] According to the vinyl anchoring adhesive provided by the present invention, the weight ratio of component A and component B satisfies the following condition: after the components A and B are mixed, the curing agent accounts for 0.6-1.6% of the total weight of the mixture.

[0028] The vinyl-type anchoring adhesive provided by the present invention has a maximum pull-out force of 222-284 kN, a bending strength of 51-67 MPa, and a compressive strength of 70-93 MPa.

[0029] On the other hand, the present invention also provides a method for preparing the vinyl-type anchoring adhesive.

[0030] In some embodiments of the present invention, the preparation method comprises the following steps:

[0031] (1) Preparation of Component A: First, place the resin solution into a stirred kettle, heat it to 60-65°C, control the speed at 300-500 rpm, gradually add the polymerization inhibitor and accelerator, and stir for 15-20 minutes to prepare a pre-accelerated unsaturated polyester resin solution. Then, add the penetrant and stir under vacuum for 5-8 minutes, and control the pressure at -0.06 to -0.10 MPa. Pump the above mixed solution into a kneading kettle, control the kneading kettle speed at 50-60 rpm, gradually add the anti-settling agent and filler I, and stir for 45-50 minutes to prepare Component A.

[0032] (2) Preparation of component B: At room temperature, first add the curing agent to the kneading kettle and disperse it evenly, then add filler II and stir for 50-60 minutes to prepare component B.

[0033] The vinyl-type rebar-anchoring adhesive provided by the present invention has flame retardancy and significantly improved mechanical properties compared with existing rebar-anchoring adhesives by adding a specific penetrant, thereby greatly improving its safety and reliability.

[0034] Furthermore, through the improvement of the curing agent, the anchor glue provided by the present invention can reach the construction strength in a short time, shortening the construction period and significantly improving work efficiency. DETAILED DESCRIPTION

[0035] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0036] Unless otherwise specified, all reagents used in the following examples and comparative examples are commercially available. The penetrants were purchased from BYK Chemie, Germany. The acidic polymer alkylammonium salt solution was BYK-140, the salt solution of long-chain polyamine amide and polar acidic ester was BYK-101, the polyether-modified polydimethylsiloxane was BYK-331, the polyacrylate copolymer was BYK-359, and the fatty alcohol polyoxyethylene ether was BYK-204.

[0037] Examples 1-7 and Comparative Examples 1-16

[0038] Provided are vinyl-type anchor glues, including component A and component B. The specific composition of component A is shown in Table 1-2, and the composition of component B is the same as shown in Table 3, wherein the data in the table are parts by weight.

[0039] Follow the steps below to produce component A and component B of the anchor glue:

[0040] (1) Preparation of Component A: First, place the resin solution into a stirred kettle, heat it to 60-65°C, control the speed at 300-500 rpm, gradually add the polymerization inhibitor and accelerator, and stir for 15-20 minutes to prepare a pre-accelerated unsaturated polyester resin solution. Then, add the penetrant and stir under vacuum for 5-8 minutes, and control the pressure at -0.06 to -0.10 MPa. Pump the above mixed solution into a kneading kettle, control the kneading kettle speed at 50-60 rpm, gradually add the anti-settling agent and filler I, and stir for 45-50 minutes to prepare Component A.

[0041] (2) Preparation of component B: At room temperature, first add the curing agent to the kneading kettle and disperse it evenly, then add filler II and stir for 50-60 minutes to prepare component B.

[0042] When used, the weight ratio of A:B is 10:1, so that the curing agent accounts for 0.6-1.6% of the total weight of the mixture of components A and B.

[0043] Table 1

[0044]

[0045]

[0046] Table 2

[0047]

[0048]

[0049] Table 3

[0050]

[0051] The properties of the rebar-anchoring adhesive prepared above were tested in accordance with GB 50367-2013 "Code for Design of Reinforcement of Concrete Structures," GB / T2570 "Test Method for Flexural Properties of Resin Castings," and GB / T2569 "Test Method for Compression Properties of Resin Castings." The concrete strength grade used was C30, and the rebar was HPB300 hot-rolled round steel bars with a diameter of 25 mm and an implant depth of 200 mm. After curing for 7 days, the maximum pull-out force and failure mode were measured. The performance indicators are listed in the table below.

[0052] Table 4

[0053]

[0054]

[0055] Examples 8-17 and Comparative Examples 17-24

[0056] A vinyl anchoring adhesive is provided, comprising component A and component B, wherein component A is the same as component A in Example 4, and component B is shown in the following table. The preparation method is the same as above.

[0057] Table 5

[0058]

[0059] The rebar-anchoring adhesive obtained above was tested for performance using the same testing method as above. Ten samples were tested for each group, with five samples tested after one day and five after seven days, and the average values ​​were taken. The mechanical properties are shown in the table below.

[0060] Table 6

[0061]

[0062] Examples 18-27

[0063] A vinyl anchoring adhesive is provided, comprising component A and component B, with specific compositions shown in Table 7 and Table 8. The preparation method is the same as above.

[0064] Table 7

[0065]

[0066]

[0067] Table 8

[0068]

[0069]

[0070] The properties of the rebar-anchoring adhesive prepared above were tested one day later using the same testing methods as before. The oxygen index was also tested according to GB / T2046-2009 "Determination of Oxygen Index Method," and the results are shown in the following table.

[0071] Table 9

[0072]

[0073]

[0074] From the experimental results in Table 4 above, it can be seen that the addition of an appropriate amount of penetrant significantly improves the maximum pull-out force, i.e., the bonding force, of the rebar-anchoring adhesive, but has little effect on the bending strength and compressive strength of the rebar-anchoring adhesive. From comparative examples 1-16, it can be seen that the addition of two of the penetrants, namely, the acidic polymer alkyl ammonium salt solution, the salt solution of long-chain polyamine amide and polar acidic ester, and polyether-modified polydimethylsiloxane, to the rebar-anchoring adhesive slightly increases its bonding performance, but the effect is not obvious. By using the three penetrants in combination, the bonding force of the rebar-anchoring adhesive is significantly improved, and the performance decreases with the excessive addition of penetrants. The combined use of penetrants can effectively reduce the surface tension of the adhesive, giving it good fluidity and permeability, and can fully wet the stone surface and penetrate into tiny gaps before the colloid gels, greatly improving the bonding area of ​​the adhesive. Excessive addition of penetrants has a certain effect on its mechanical properties. At the same time, the experimental results show that the optimal ratio of the three penetrants, namely, acidic polymer alkyl ammonium salt solution, long-chain polyamine amide and polar acidic ester salt solution, and polyether-modified polydimethylsiloxane, is 2:3:1, and the optimal total dosage is 7.2 parts.

[0075] Comparing the experimental results in Table 6 above, it can be seen that the mechanical properties of Comparative Examples 17 and 18 were relatively poor in all aspects after one day. At this time, the resin in the colloid was still in the reaction stage and had not fully polymerized. After curing for 7 days, it could meet the use standard. By comparing Comparative Examples 19-24, Examples 8-12, and Example 16, the combination of diacyl peroxide and hydroperoxide showed significant improvement in all mechanical properties after one day of curing, indicating that the curing agent combination effectively shortened the curing time of the anchoring glue. After 7 days of curing, the mechanical properties of the anchoring glue with the combination of curing agents were also improved compared to the single curing agent anchoring glue. This is mainly due to the higher exothermic peak and initiation activity after the combination of diacyl peroxide and hydroperoxide, which enables the resin in the anchoring glue to react quickly, efficiently and fully. Comparing Comparative Examples 21-24, Examples 8-10, and Example 16, it can be seen that the best effect is achieved when benzoyl peroxide and isopropylbenzene hydroperoxide are used together. Experiments show that hydroperoxide alone does not initiate polymerization in this system, so this invention does not compare it separately. By comparing Examples 11, 12, 16 with Comparative Examples 19 and 20, it can be seen that the optimal ratio of benzoyl peroxide and cumene hydroperoxide is 1:1.

[0076] From the experimental results in Table 9 above, it can be seen that the anchor glue obtained by the present invention has excellent mechanical properties after one day and also has a good flame retardant effect.

[0077] In summary, the present invention provides a fast, efficient, high-strength flame-retardant anchor glue, which can better meet current social needs compared with existing anchor glues.

[0078] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A vinyl type anchoring glue, characterized in that: The invention comprises a component A and a component B, wherein the component A comprises a vinyl ester unsaturated polyester resin, a bisphenol A type unsaturated polyester resin, a dicyclopentadiene type unsaturated polyester resin, a reactive diluent, a filler I and a penetrant, wherein the penetrant comprises, by weight, 20-40 parts of an acidic polymer alkylammonium salt solution, 35-60 parts of a salt solution of a long-chain polyamine amide and a polar acidic ester, and 15-35 parts of a polyether-modified polydimethylsiloxane; The B component includes a curing agent, which is a composition of diacyl peroxide and hydroperoxide; The mass of the penetrant accounts for 3-11% of the total mass of the unsaturated polyester resin; The active diluent is a mixture of a chlorine-containing active diluent and a phosphorus-containing active diluent, wherein the mass ratio of the chlorine-containing active diluent to the phosphorus-containing active diluent is between 1:4 and 4:

1.

2. The vinyl anchoring adhesive according to claim 1, characterized in that: The chlorine-containing active diluent is 2,5-dichlorostyrene and / or 2,6-dichlorostyrene; And / or, the phosphorus-containing reactive diluent is one or more of triallyl phosphate, diallyl phenyl phosphate, diallyl octyl phosphate and diallyl cresyl phosphate.

3. The vinyl anchoring adhesive according to claim 2, characterized in that: In parts by weight, the component A comprises: 60-85 parts of vinyl ester unsaturated polyester resin, 10-25 parts of bisphenol A type unsaturated polyester resin, 5-15 parts of dicyclopentadiene type unsaturated polyester resin, 25-35 parts of active diluent, 100-300 parts of filler I and 3-12 parts of penetrant.

4. The vinyl anchoring adhesive according to claim 3, characterized in that: The component A further comprises: 0.015-0.08 parts of polymerization inhibitor, 0.15-0.8 parts of accelerator and 3-8 parts of anti-settling agent.

5. The vinyl anchoring adhesive according to claim 4, characterized in that: The B component includes a curing agent, which is a composition of diacyl peroxide and hydroperoxide.

6. The vinyl anchoring adhesive according to claim 5, characterized in that: The diacyl peroxide is selected from one or more of benzoyl peroxide and dilauroyl peroxide; the hydroperoxide is selected from one or more of cumene hydroperoxide and tert-butyl hydroperoxide; the mass ratio of the diacyl peroxide to the hydroperoxide is between 1:2 and 2:

1.

7. The vinyl anchoring adhesive according to claim 6, characterized in that: The weight ratio of the component A to the component B satisfies the following condition: after the components A and B are mixed, the curing agent accounts for 0.6-1.6% of the total weight of the mixture.

8. The vinyl anchoring adhesive according to any one of claims 1 to 7, characterized in that: The vinyl-type anchor glue has a maximum pull-out force of 222-284 kN, a bending strength of 51-67 MPa, a compressive strength of 70-93 MPa, and a flame retardant oxygen index of 37-42%.

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