阅读说明：本技术 一种环保型石材背筋胶及其制备方法 (Environment-friendly stone back bar adhesive and preparation method thereof ) 是由 杜昆文 杜昆武 邱国峰 王莉亚 熊善高 毛攀峰 季亦同 于 2020-11-12 设计创作，主要内容包括：本发明提供一种环保型石材背筋胶及其制备方法,所述环保型石材背筋胶包括A组分和B组分,A组分包括环保型不饱和聚酯树脂和抗收缩增韧剂,B组分包括过氧化物引发剂；所述抗收缩增韧剂包括由甲基乙烯基硅橡胶生胶与天然橡胶生胶混炼后溶于石油醚中形成的糊状物,所述抗收缩增韧剂占环保型不饱和聚酯树脂的质量百分比为5-15％。本发明的环保型石材背筋胶以不饱和聚酯树脂作为基体,可以充分给予胶体优良的耐水耐酸性能,加入由甲基乙烯基硅橡胶生胶与天然橡胶生胶混炼后溶于石油醚中形成的糊状物,可大大提高环保型石材背筋胶的韧性,同时还能提升抗收缩性能,从而不需要额外添加抗收缩剂,获得了综合力学性能优良的环保型石材背筋胶。(The invention provides an environment-friendly stone back bar adhesive and a preparation method thereof, wherein the environment-friendly stone back bar adhesive comprises a component A and a component B, the component A comprises an environment-friendly unsaturated polyester resin and an anti-shrinkage toughening agent, and the component B comprises a peroxide initiator; the anti-shrinkage toughening agent comprises paste formed by mixing raw methyl vinyl silicone rubber and raw natural rubber and dissolving the mixture in petroleum ether, and the anti-shrinkage toughening agent accounts for 5-15% of the environment-friendly unsaturated polyester resin by mass. The environment-friendly stone back bar adhesive disclosed by the invention takes unsaturated polyester resin as a matrix, can fully provide excellent water resistance and acid resistance to the adhesive, and can greatly improve the toughness of the environment-friendly stone back bar adhesive and simultaneously improve the anti-shrinkage performance by adding a paste formed by mixing raw methyl vinyl silicone rubber and raw natural rubber and dissolving the mixture in petroleum ether, so that the environment-friendly stone back bar adhesive with excellent comprehensive mechanical properties is obtained without additionally adding an anti-shrinkage agent.)

1. The environment-friendly stone back bar adhesive is characterized by comprising a component A and a component B, wherein the component A comprises environment-friendly unsaturated polyester resin and an anti-shrinkage toughening agent, and the component B comprises a peroxide initiator;

the anti-shrinkage toughening agent comprises paste formed by mixing raw methyl vinyl silicone rubber and raw natural rubber and dissolving the mixture in petroleum ether, and the anti-shrinkage toughening agent accounts for 5-15% of the environment-friendly unsaturated polyester resin by mass.

2. The environment-friendly stone back bar adhesive as claimed in claim 1, wherein the weight ratio of the raw methyl vinyl silicone rubber to the raw natural rubber is 1:3-3: 1;

and/or the weight ratio of the rubber raw rubber and the petroleum ether after mixing is 3:2-4: 1.

3. The environment-friendly stone back bar adhesive according to claim 1, wherein the environment-friendly unsaturated polyester resin is composed of a styrene-free unsaturated polyester resin and a reactive diluent in a weight ratio of 3:2-4:1, and the reactive diluent is one or more of ethylene glycol dimethacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate, and tripropylene glycol diacrylate.

4. The environment-friendly stone back bar glue according to any one of claims 1 to 3, wherein the component A further comprises a first filler and a leveling agent; the component B also comprises a blending agent and a second filler; the peroxide initiator accounts for 0.5-3.5% of the total weight of the component A and the component B.

5. The environment-friendly stone back bar adhesive according to claim 4, wherein the leveling agent is a silane-based leveling agent, and the first filler comprises lipophilic active filler and silica powder.

6. The environment-friendly stone back bar adhesive as claimed in claim 5, wherein the silane leveling agent is one or more of polydimethylsiloxane, polymethylphenylsiloxane, polyether-modified dimethylsiloxane and polyester-modified dimethylsiloxane;

and/or the lipophilic active filler is one or more of activated calcium carbonate, activated barium sulfate and activated aluminum hydroxide, and the weight ratio of the lipophilic active filler to the silicon powder is 4:1-9: 1.

7. The environment-friendly stone back bar adhesive as claimed in claim 4, wherein the peroxide initiator is one or more of benzoyl peroxide, diacetyl peroxide, tert-butyl peroxybenzoate, 2, 4-dichlorobenzoyl peroxide and lauroyl peroxide;

and/or the blending agent is one or more of dibutyl phthalate, dimethyl phthalate, pentadecane, isododecane and ethyl acetate;

and/or the second filler is one or more of calcium stearate, zinc stearate, magnesium stearate and aluminum stearate.

8. The environment-friendly stone back bar adhesive according to claim 4, which comprises a component A and a component B, wherein the component A comprises 100 parts by weight of environment-friendly unsaturated polyester resin, 5-15 parts by weight of anti-shrinkage toughening agent, 40-125 parts by weight of lipophilic active filler, 10-30 parts by weight of silicon powder and 2-8 parts by weight of silane leveling agent; the component B comprises 40-60 parts of peroxide initiator, 20-30 parts of blender and 20-30 parts of second filler; the peroxide initiator accounts for 0.5-3.5% of the total weight of the component A and the component B.

9. The environment-friendly stone back bar adhesive according to claim 8, comprising a component A and a component B, wherein the component A comprises 100 parts by weight of environment-friendly unsaturated polyester resin, 8-15 parts by weight of anti-shrinkage toughening agent, 40-125 parts by weight of lipophilic active filler, 10-15 parts by weight of silicon powder and 2-8 parts by weight of silane leveling agent; the component B comprises 40-60 parts of peroxide initiator, 20-30 parts of blender and 20-30 parts of second filler;

the shrinkage-resistant toughening agent is formed by mixing raw methyl vinyl silicone rubber and raw natural rubber in a weight ratio of 1:3-3:1 and dissolving the mixture in petroleum ether, wherein the weight ratio of the mixed raw rubber to the petroleum ether is 3:2-4: 1.

10. The method for preparing environment-friendly stone back bar glue of any one of claims 1-9, characterized by comprising:

stirring and mixing the raw materials of the component A under a negative pressure state, and extruding by a double screw to obtain the component A;

and stirring and mixing the raw materials of the component B under a negative pressure state to obtain the component B.

Technical Field

The invention relates to the technical field of building materials, in particular to an environment-friendly stone back bar adhesive and a preparation method thereof.

Background

In the field of building materials, the back ribs of the stone refer to that after the stone is cut into plates, in order to avoid damage or fracture in the processes of transportation, operation and the like, grooves are formed in the back of the stone, and reinforcing steel bars are added, so that the stone has better firmness. The stone back bar glue is used for fixing the reinforcing steel bars, and plays a vital role in ensuring the quality of the stone as the glue for reinforcement.

The stone back rib reinforcement at the present stage is mainly made of white cement or marble adhesive, but the white cement or the marble adhesive has some disadvantages. The cement has long curing time, which affects the construction, and at least one week of water adding and curing time is needed, so that the stone is easy to have pathological changes in a humid environment, such as water spots, bloom, wet marks and the like, which affects the appearance; and the cement is prevented from being corroded by acid, acidic substances and calcium hydroxide in the cement can generate neutralization reaction, and the generated objects are loose and expanded and are easy to hydrolyze and pulverize after meeting water, so that the reinforcing steel bars fall off. The marble glue has the problems of large shrinkage rate and brittle performance after curing, and the marble glue is generally viscous paste, is not easy to level in the stone grooving and is not beneficial to construction. In addition, the active diluents of the unsaturated polyester resin used in the existing marble glue are all styrene, and the styrene is easy to volatilize to form 'ice slush' (self-aggregation generated by styrene volatilization), so that the storage stability of the glue is influenced; and the volatilized styrene can pollute the environment and damage the health of construction operators.

Disclosure of Invention

The invention provides an environment-friendly stone back bar adhesive and a preparation method thereof.

The embodiment of the invention provides an environment-friendly stone back bar adhesive, which comprises a component A and a component B, wherein the component A comprises an environment-friendly unsaturated polyester resin and an anti-shrinkage toughening agent, the component B comprises a peroxide initiator, the anti-shrinkage toughening agent comprises a paste formed by mixing methyl vinyl silicone rubber raw rubber and natural rubber raw rubber and dissolving the mixture in petroleum ether, and the anti-shrinkage toughening agent accounts for 5-15% of the environment-friendly unsaturated polyester resin by mass.

The environment-friendly stone back rib adhesive takes environment-friendly unsaturated polyester resin as matrix resin, has low elongation and larger brittleness after being cured, is easy to generate cracks when a bonding part bears external force, and rapidly expands to cause the cracking of an adhesive layer, is not fatigue-resistant, and cannot be used for structural bonding. Therefore, a toughening agent is usually added to the raw materials to reduce brittleness and increase toughness. Liquid nitrile rubber, polyvinyl butyral, polyvinyl acetate and the like are generally selected for the unsaturated polyester resin adhesive, but the toughening agents are tried, and the expected effect cannot be achieved.

Through a large number of experiments, the inventor finds that the toughness of the environment-friendly stone back bar adhesive can be effectively improved and the environment-friendly stone back bar adhesive is not easy to break by dissolving a paste formed by mixing raw methyl vinyl silicone rubber and raw natural rubber in petroleum ether. Experiments also find that after the paste is used as a toughening agent, the anti-shrinkage performance of the environment-friendly stone back bar adhesive can be obviously improved, and a good anti-shrinkage effect can be achieved without additionally adding an anti-shrinkage agent.

Preferably, the weight ratio of the raw methyl vinyl silicone rubber to the raw natural rubber is 1:3-3: 1.

Preferably, the weight ratio of the rubber raw rubber and the petroleum ether after mixing is 3:2-4: 1.

Specifically, the preparation of the anti-shrinkage toughening agent can adopt the following method:

(1) mixing raw methyl vinyl silicone rubber and raw natural rubber for 2-3h in a double-roller open mill according to the weight ratio of 1:3-3:1, so that the raw rubber is fully and uniformly mixed, and the roller temperature is controlled below 40 ℃;

(2) and placing the mixed colloid in petroleum ether, and standing for 24h for full dissolution, wherein the weight ratio of the mixed raw rubber to the petroleum ether is 3:2-4: 1.

In addition, the invention adopts the environment-friendly unsaturated polyester resin to replace the unsaturated polyester resin which needs to be diluted by styrene, thereby avoiding the phenomenon of ice slush, improving the stability of the storage and construction of the stone back bar adhesive, simultaneously improving the safety performance of the adhesive and reducing the harm to the human body and the environment.

Preferably, the environment-friendly unsaturated polyester resin consists of styrene-free unsaturated polyester resin and a reactive diluent in a weight ratio of 3:2-4:1, wherein the reactive diluent is one or more of ethylene glycol dimethacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol diacrylate and tripropylene glycol diacrylate.

Preferably, the A component further comprises a first filler and a leveling agent; the component B also comprises a blending agent and a second filler; the peroxide initiator accounts for 0.5-3.5% of the total weight of the component A and the component B.

Preferably, the leveling agent is a silane leveling agent, and the first filler comprises lipophilic active filler and silicon powder.

The lipophilic active filler has good compatibility with unsaturated polyester resin and excellent dispersion performance, and can be stably dispersed in the unsaturated polyester resin without adding anti-settling agents such as hydrogenated castor oil, fumed silica, precipitation-process silica and the like. The silane leveling agent has low surface tension, can migrate to the surface of the adhesive layer, and has the effects of controlling the surface flow of the adhesive layer and promoting the leveling. Experiments show that the silane leveling agent used in the invention can improve the comprehensive mechanical property of the environment-friendly stone back bar adhesive in the presence of silicon powder.

Preferably, the mesh number of the first filler is 400-1250 mesh.

Preferably, the silane leveling agent is one or more of polydimethylsiloxane, polymethylphenylsiloxane, polyether modified dimethylsiloxane and polyester modified dimethylsiloxane.

Preferably, the lipophilic active filler is one or more of activated calcium carbonate, activated barium sulfate and activated aluminum hydroxide, and the weight ratio of the lipophilic active filler to the silicon powder is 4:1-9: 1.

In the technical scheme, the peroxide initiator is one or more of benzoyl peroxide, diacetyl peroxide, tert-butyl peroxybenzoate, 2, 4-dichlorobenzoyl peroxide and lauroyl peroxide.

The blender is one or more of dibutyl phthalate, dimethyl phthalate, pentadecane, isododecane and ethyl acetate.

The second filler is one or more of calcium stearate, zinc stearate, magnesium stearate and aluminum stearate.

Specifically, the environment-friendly stone back bar adhesive provided by the embodiment of the invention comprises a component A and a component B, wherein the component A comprises 100 parts by weight of environment-friendly unsaturated polyester resin, 5-15 parts by weight of anti-shrinkage toughening agent, 40-125 parts by weight of lipophilic active filler, 10-30 parts by weight of silicon powder and 2-8 parts by weight of silane leveling agent; the component B comprises 40-60 parts of peroxide initiator, 20-30 parts of blender and 20-30 parts of second filler; the peroxide initiator accounts for 0.5-3.5% of the total weight of the component A and the component B.

In a preferred embodiment of the invention, the environment-friendly stone back bar glue comprises a component A and a component B, wherein the component A comprises 100 parts by weight of environment-friendly unsaturated polyester resin, 8-15 parts by weight of anti-shrinkage toughening agent, 40-125 parts by weight of lipophilic active filler, 10-15 parts by weight of silicon powder and 2-8 parts by weight of silane leveling agent; the component B comprises 40-60 parts of peroxide initiator, 20-30 parts of blender and 20-30 parts of second filler;

the shrinkage-resistant toughening agent is formed by mixing raw methyl vinyl silicone rubber and raw natural rubber in a weight ratio of 1:3-3:1 and dissolving the mixture in petroleum ether, wherein the weight ratio of the mixed raw rubber to the petroleum ether is 3:2-4: 1.

The embodiment of the invention also provides a preparation method of the environment-friendly stone back bar adhesive, which comprises the following steps:

stirring and mixing the raw materials of the component A under a negative pressure state, and extruding by a double screw to obtain the component A;

and stirring and mixing the raw materials of the component B under a negative pressure state to obtain the component B.

Specifically, the environment-friendly stone back bar adhesive can be prepared by the following preparation method:

adding the component A into a stirring kettle, stirring at vacuum degree of 0.08-0.1Mpa and rotation speed of not less than 1500r/min for 15-25min, stirring and dispersing in a pipeline of a double-screw extruder, continuously extruding with a main screw at rotation speed of not less than 100r/min by using a driving screw, and adding CO₂A two-phase cooling system, wherein the discharging temperature is controlled to be not higher than 30 ℃ to obtain a component A;

and putting the raw materials of the component B into a stirring kettle, and stirring for 15-25min under the negative pressure state that the vacuum degree is 0.08-0.1Mpa and the rotating speed is not less than 1500r/min to obtain the component B.

The environment-friendly stone back bar adhesive provided by the embodiment of the invention takes environment-friendly unsaturated polyester resin as a matrix, can fully provide excellent water resistance and acid resistance for the adhesive, is added with paste formed by mixing raw methyl vinyl silicone rubber and raw natural rubber and dissolving the mixture in petroleum ether, can greatly improve the toughness of the environment-friendly stone back bar adhesive, and can also improve the anti-shrinkage performance of the environment-friendly stone back bar adhesive, so that an additional anti-shrinkage agent is not required, the toughening and anti-shrinkage integration is realized, and the stone back bar adhesive with excellent comprehensive mechanical properties is obtained. The silane leveling agent is added into the environment-friendly stone back bar adhesive, so that the environment-friendly stone back bar adhesive has good leveling property and is easy to construct and operate, and experiments show that the comprehensive mechanical property of the environment-friendly stone back bar adhesive can be improved. In addition, the invention adopts the environment-friendly unsaturated polyester resin to replace the unsaturated polyester resin which needs to be diluted by styrene, thereby avoiding the phenomenon of ice slush, improving the stability of the storage and construction of the stone back bar adhesive, simultaneously improving the safety performance of the adhesive and reducing the harm to the human body and the environment.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The materials used in the following examples are commercially available unless otherwise specified.

Example 1

The embodiment provides an environment-friendly stone back rib adhesive, which comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 70 parts of styrene-free unsaturated polyester resin, 10 parts of ethylene glycol dimethacrylate, 20 parts of 1, 6-hexanediol diacrylate, 10 parts of anti-shrinkage toughening agent, 50 parts of active calcium carbonate, 50 parts of active barium sulfate, 15 parts of silicon powder, 2 parts of polydimethylsiloxane and 3 parts of polyester modified dimethyl siloxane; the component B comprises the following components: 30 parts of benzoyl peroxide, 10 parts of tert-butyl peroxybenzoate, 20 parts of dibutyl phthalate, 20 parts of calcium stearate and 10 parts of zinc stearate;

the preparation method of the anti-shrinkage toughening agent comprises the following steps: (1) mixing raw methyl vinyl silicone rubber and raw natural rubber for 2-3h in a double-roller open mill according to the weight ratio of 1:1, so that the raw rubber is fully and uniformly mixed, and the roller temperature is controlled below 40 ℃; (2) and (3) putting the mixed raw rubber into petroleum ether, standing for 24 hours for full dissolution, wherein the weight ratio of the mixed rubber to the petroleum ether is 3: 2.

The embodiment also provides a preparation method of the environment-friendly stone back bar adhesive, which comprises the following steps:

adding the above components A into a stirring kettle, stirring at vacuum degree of 0.08-0.1Mpa and rotation speed of not less than 1500r/min for 15-25min, stirring and dispersing in a double screw extruder, and mixing with active screwThe rod is continuously extruded, the rotating speed of the main screw is not less than 100r/min, and CO is adopted₂And a two-phase cooling system, wherein the discharging temperature is controlled to be not higher than 30 ℃.

Putting the raw materials of the component B into a stirring kettle, and stirring for 15-25min under the vacuum degree of 0.08-0.1Mpa and the rotation speed of not less than 1500 r/min.

When the curing agent is used, A, B components are uniformly mixed, the mass ratio of the peroxide initiator after mixing is guaranteed to be 0.5-3.5%, the curing agent is filled in the stone groove, and then steel bars are implanted for maintenance and curing.

Examples 2-12 and comparative examples 1-7 also provide an environment-friendly type stone back bar adhesive, which has a composition different from that of example 1, specifically shown in tables 1 and 2.

Table 1 composition of environment-friendly type stone back-rib glue for each example

Table 1 composition of environment-friendly stone back-rib glue for each example (continue)

TABLE 2 composition of environmentally friendly stone back-rib glue in each proportion

TABLE 2 Environment-friendly Stone back bar glue compositions (continuance) in each proportion

The bending elastic modulus, impact toughness and compression shear bonding strength (standard and water immersion) of the cured product of the environment-friendly stone back bar adhesive in each example and each comparative example are tested by referring to a test method of a building material industry standard JC/T989-2016 of the people's republic of China. Meanwhile, the total volume shrinkage is tested by referring to the method of ISO 3521-1997 determination of the total volume shrinkage of the plastic unsaturated polyester and the epoxy resin; the test results are shown in table 3.

TABLE 3 Performance test data of environmental protection type Stone back bar glue

As can be seen from Table 3, the environment-friendly stone back bar adhesive provided by the embodiment of the invention is superior to a comparative example in the aspects of comprehensive mechanical property, shrinkage resistance and the like, and meanwhile, has good leveling property and is easy to construct and operate. After the anti-shrinkage toughening agent is added, the comprehensive mechanical properties, particularly the impact toughness and the anti-shrinkage property are greatly improved (the embodiment 11 and the comparative example 2 are combined); meanwhile, the anti-shrinkage toughening agent and the leveling agent are added, so that the comprehensive mechanical property is improved more obviously, and a synergistic effect is probably generated between the anti-shrinkage toughening agent and the leveling agent (combining examples 11-12 and comparative example 2); experiments show that the silicon powder can improve the mechanical property of the environment-friendly stone back bar adhesive to a certain extent, and the silane leveling agent used in the invention can further improve the comprehensive mechanical property of the environment-friendly stone back bar adhesive in the presence of the silicon powder (in combination with the embodiment 11 and the comparative examples 1-3). Meanwhile, by combining example 11 and comparative examples 4 to 5, it can be found that the shrinkage resistance effect can be achieved after the methyl vinyl silicone rubber crude rubber and the natural rubber crude rubber are added simultaneously, and the mechanical properties are further improved; by combining the example 11 and the comparative examples 6 to 7, it can be found that the toughening effect of the added liquid nitrile rubber (toughening agent) is obviously inferior to the toughening effect of the added anti-shrinkage toughening agent, and the anti-shrinkage effect can not be achieved, and the mechanical comprehensive performance and anti-shrinkage performance of the added liquid nitrile rubber (toughening agent) and the added polystyrene (anti-shrinkage agent) are inferior to the mechanical comprehensive performance and anti-shrinkage performance of the added anti-shrinkage toughening agent. It is worth noting that the inventors have conducted experiments using a number of toughening and anti-shrinking agents, all of which are similar to comparative examples 6-7.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.