CN107090264B - Toughened environment-friendly back mesh adhesive as well as preparation method and application thereof - Google Patents
Toughened environment-friendly back mesh adhesive as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN107090264B CN107090264B CN201710481453.4A CN201710481453A CN107090264B CN 107090264 B CN107090264 B CN 107090264B CN 201710481453 A CN201710481453 A CN 201710481453A CN 107090264 B CN107090264 B CN 107090264B
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- agent
- unsaturated polyester
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a toughened environment-friendly back mesh adhesive and a preparation method thereof, wherein a component A comprises 45-65 parts of dicyclopentadiene modified unsaturated polyester resin, 25-40 parts of bisphenol A epoxy vinyl resin, 10-15 parts of hyperbranched unsaturated polyester, 1-2.5 parts of a dispersing agent, 5-10 parts of a core-shell particle toughening agent, 25-40 parts of spherical silicon micro powder, 15-25 parts of nano calcium carbonate, 0.2-0.8 part of an accelerator and 0.02-0.08 part of a polymerization inhibitor. The component B consists of 10-70 parts of curing agent, 30-40 parts of blending agent, 30-50 parts of inorganic filler and 3-10 parts of stabilizing agent, and the curing agent accounts for 0.5-3.5% of the total weight of the mixture after the component A and the component B are mixed. The back net glue has the advantages of small viscosity, good permeability, moderate rheological property, low content of total Volatile Organic Compounds (VOCs), and obviously superior mechanical strength, especially impact resistance, to the prior product.
Description
Technical Field
The invention belongs to the field of stone adhesives, and particularly relates to a two-component room temperature curing toughening type environment-friendly back mesh adhesive and a preparation method thereof.
Background
Natural stone such as marble, etc. have been widely used for indoor and outdoor decoration of buildings and homes, and among them, the most widely used stone is veneer stone slab. High-grade natural stone materials are limited in resources, cannot be regenerated and are increasingly expensive, and the thin development of plate materials cannot be avoided; since the stone is uneven and fragile in natural structure, the technical measure of reinforcing the back of the thin plate by sticking the back of the thin plate by a back net method is brought forward.
Several varieties of adhesives for adhering mesh fabrics are sold on the market in recent years, one is a compound of a water-based adhesive, cement and a filler, and the material has low price, but has poor strength, poor corrosion resistance and poor aging resistance; the other is a solvent-type unsaturated polyester adhesive, which has the advantages of fast curing, high construction efficiency, low strength, poor adhesion, large shrinkage, high toxicity and no contribution to indoor construction of back mesh adhesives; the other is a common epoxy adhesive, such as 'a modified epoxy stone back mesh adhesive and a preparation method thereof' described in application No. 201410014834.8, which has high bonding strength and good aging resistance, but has long curing time, low construction efficiency and large shrinkage rate, and needs to be improved. The adhesive has the common defects of high brittleness and insufficient toughness when being used for the back net of the stone, so that the stone after the back net is adhered still breaks in the processing process.
Disclosure of Invention
In order to overcome the defects, the invention provides a double-component toughened environment-friendly back mesh adhesive and a preparation method and application thereof.
In order to achieve the above object, according to one aspect of the present invention, there is provided a toughened type environment-friendly back mesh adhesive, which includes a component a, wherein the component a includes, by weight: 45-65 parts of dicyclopentadiene modified unsaturated polyester resin, 25-40 parts of bisphenol A epoxy vinyl resin, 10-15 parts of hyperbranched unsaturated polyester, 1-2.5 parts of dispersing agent, 5-15 parts of core-shell particle toughening agent, 25-40 parts of spherical silicon micro powder, 15-25 parts of nano calcium carbonate, 0.2-0.8 part of accelerator and 0.02-0.08 part of polymerization inhibitor.
Preferably, the back mesh adhesive further comprises a component B, wherein the component B comprises the following components in parts by weight: 10-70 parts of curing agent, 30-40 parts of blending agent, 30-50 parts of inorganic filler and 3-10 parts of stabilizing agent.
Preferably, the weight ratio of the component A to the component B meets the following conditions: the A component and the B component are mixed to ensure that the curing agent accounts for 0.5-3.5% of the total weight of the mixture.
Preferably, the core-shell particle toughening agent is one or more of polymethyl methacrylate-polybutadiene core-shell particles, core-shell rubber particles and organosilicon core-shell particles.
Preferably, the hyperbranched unsaturated polyester is one or two of hyperbranched unsaturated resin and hyperbranched vinyl ester resin.
Preferably, the mesh number of the spherical silicon micro powder is 800-2000 meshes.
Preferably, the dispersant is selected from
5215. One or more of a special dispersant 3219, BYK-P104S and BYK-142 for the composite material.
Preferably, the accelerator is one or more of N, N-dimethylaniline, N-diethylaniline, N-dimethyl-p-toluidine, N-methyl-N-hydroxyethylaniline, N-methyl-N-hydroxyethyl-p-toluidine, N-methyl-N-hydroxypropyl-p-toluidine, N-dihydroxyethylaniline and homologues thereof.
Preferably, the polymerization inhibitor is one or more of hydroquinone, 2, 5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone and 4-tert-butyl catechol.
Preferably, the curing agent is one or more of benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, 2, 4-dichlorobenzoyl peroxide and lauroyl peroxide.
Preferably, the blending agent is one or more of dibutyl phthalate, dimethyl phthalate, pentadecane, isododecane and ethyl acetate.
Preferably, the inorganic filler is one or more of calcium carbonate, activated barium sulfate, activated calcium carbonate, silica and aluminum hydroxide.
Preferably, the stabilizer is one or more of calcium stearate, cadmium stearate, zinc stearate and lead stearate.
According to another aspect of the invention, a preparation method of the toughening type environment-friendly back mesh adhesive is provided, which comprises the following steps:
(1) preparation of component A: adding dicyclopentadiene modified unsaturated polyester resin, bisphenol A type vinyl epoxy resin and hyperbranched unsaturated polyester into a reaction kettle, adding a dispersing agent, stirring for 30-45 minutes under a heating condition, then adding pretreated spherical silicon micro powder, nano calcium carbonate, an accelerator, a polymerization inhibitor and a core-shell particle flexibilizer, after adding the materials, heating to 60-80 ℃, vacuumizing to-0.1 Mpa, keeping vacuum high-speed stirring for 1500-2000 r/min, keeping the temperature for ultrasonic dispersion for 45 minutes, then cooling to 20-40 ℃, stopping stirring, discharging, filtering by a 100-mesh 200-mesh filter screen, packaging and sealing to obtain the component A of the invention;
(2) preparation of the component B: adding the curing agent, the blending agent, the stabilizing agent and the inorganic filler into a reaction kneading kettle in sequence under the condition of stirring, continuing stirring for 1-2 hours after the materials are added, stopping stirring, discharging, packaging and sealing to obtain the component B.
According to another aspect of the invention, the application of the toughening type environment-friendly back net glue is provided, and the toughening type environment-friendly back net glue is applied to bonding and reinforcing of back net stone materials.
Preferably, the A component and the B component are mixed when in use, and the A component and the B component are mixed to ensure that the curing agent accounts for 0.5-3.5% of the total weight of the mixture of the A component and the B component.
Preferably, when the method is applied to the back net stone, the method comprises the following steps:
(1) laying a stone rough plate to be subjected to back net on a platform, and paving net cloth on the surface of the rough plate;
(2) uniformly mixing the component A and the component B to obtain the toughened environment-friendly back mesh adhesive, wherein the curing agent accounts for 0.5-3.5% of the total weight of the component A and the component B;
(3) uniformly coating the back mesh glue on the mesh cloth by using a row brush or a roller, wherein the coating amount is 200-600g/m2The back mesh glue is coated once every 2-3 minutes, the initial curing time of the back mesh glue is 3-10 minutes, and the back mesh glue can be stacked after 15 minutes.
In general, the above technical solutions contemplated by the present invention can achieve the following advantageous effects compared to the prior art.
1) The dicyclopentadiene modified unsaturated polyester resin, the bisphenol A epoxy vinyl resin and the hyperbranched unsaturated polyester are selected as main resin of the component A, the peroxide curing agent is selected as a main effective component of the component B, and carbon-carbon double bonds in the resin can be rapidly polymerized under the initiation of peroxy groups, so that the room-temperature curing speed of the back mesh adhesive is greatly increased.
2) The dicyclopentadiene modified unsaturated polyester resin, the bisphenol A epoxy vinyl resin and the hyperbranched polyester are selected for mutual matching, and the bisphenol A epoxy vinyl resin can endow the back mesh rubber with excellent rigidity strength, heat resistance and chemical resistance; the dicyclopentadiene modified unsaturated polyester resin has low viscosity and high reaction activity, reduces the usage amount of a cross-linking agent, and endows the back mesh adhesive with good toughness strength; the hyperbranched unsaturated polyester is used as a cross-linking agent and a diluent in a system to replace volatile styrene, and the flexible molecular chain segment of the hyperbranched unsaturated polyester promotes the curing rate of the adhesive while reducing the viscosity of the system, so that the curing system has a certain cross-linking network density, thereby improving the impact toughness after curing. The three components are mutually matched to endow the back mesh adhesive with more excellent impact toughness, corrosion resistance, heat resistance and weather resistance.
3) The hyperbranched unsaturated polyester is used as a cross-linking agent and a diluent in the system to replace volatile styrene, so that the low-boiling point active diluent and the styrene in the adhesive system are removed, the risk of back-net cementing of ice (columnar crystals formed by styrene volatilization and self polymerization) is greatly reduced, and the content of total Volatile Organic Compounds (VOCs) in the adhesive is greatly reduced by adding the hyperbranched unsaturated polyester.
4) The core-shell particle toughening agent and the nano-particle filler composition are selected as the reinforcing agent of the component A, the core-shell particle addition amount is low, the integral viscosity of an adhesive system is not influenced, and the core-shell particle toughening agent and the nano-particle filler composition are combined with matrix resin after the adhesive is cured and are mutually linked to form a sea-island structure and a cavity effect to play a role in energy storage; the nanofiller disperses the residual stress in the cured system. The adhesive and the preparation method greatly improve the mechanical property of the solidified back-mesh adhesive, enhance the adhesive force of the adhesive to the stone back plate and the mesh yarns, and increase the adhesive force and the adhesive strength of the adhesive layer to the main material when the back-mesh veneer stone is paved and adhered on the cement mortar surface, particularly the impact toughness is obviously improved.
5) The invention contains the filler spherical silica micropowder with higher proportion, on one hand, the curing shrinkage rate and the linear expansion coefficient of a glue layer are reduced, the increase of the whole stress of the thin stone caused by the shrinkage deformation of the back net of the stone is prevented, on the other hand, the rheological property of the back net glue is also improved, the glue is favorable for the infiltration and the adhesion of the glue to the net cloth yarns and the stone, and thus, the reinforcing effect of the back net is increased. In addition, due to the use of inorganic powder, the production cost of the back mesh adhesive is reduced.
The toughening type environment-friendly back mesh adhesive disclosed by the invention is moderate in rheological property, low in viscosity and high in permeability. When the net is carried, the natural micro-seams and holes can permeate into the thin stone and the net cloth yarns. The adhesive system has extremely low content of total Volatile Organic Compounds (VOCs), protects the atmospheric environment and the health and safety of construction users, and is suitable for producing back net stones in factories and indoor processing; the mechanical strength of the back net reinforcement is obviously improved, and particularly the impact toughness strength is high; meanwhile, the powder has high filling amount, the linear expansion coefficient is similar to that of the stone, the internal stress between the powder and the thin plate stone is small, the shrinkage rate after curing is low, and the phenomenon of integral deformation and warping of the bonded and cured back mesh stone cannot occur; the colloid has stable chemical performance, firm adhesion with ceramic matrix or cement mortar surface, and good water resistance, weather resistance and aging resistance. The adhesive quality of the back net adhesive with the main body material during reinforcement and use is obviously superior to that of other existing back net adhesives.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The toughening type environment-friendly back mesh adhesive consists of A, B two components, wherein the component A consists of 45-65 parts of dicyclopentadiene modified unsaturated polyester resin, 25-40 parts of bisphenol A type epoxy vinyl resin, 10-15 parts of hyperbranched unsaturated polyester, 1-2.5 parts of dispersing agent, 5-15 parts of core-shell particle toughening agent, 25-40 parts of spherical silicon micro powder, 15-25 parts of nano calcium carbonate, 0.2-0.8 part of accelerator and 0.02-0.08 part of polymerization inhibitor. The component B consists of 10-70 parts of curing agent, 30-40 parts of blending agent, 30-50 parts of inorganic filler and 3-10 parts of stabilizing agent. The A component and the B component are mixed to ensure that the curing agent accounts for 0.5-3.5% of the total weight of the mixture. If the proportion of the curing agent is less than 0.5 percent, the curing speed is very slow, and the effect of quick curing cannot be achieved; if the proportion of the curing agent is more than 3.5%, the curing is too fast, which is disadvantageous to the construction and the mechanical properties of the cured product are also reduced.
Further, the core-shell particle toughening agent is a mixture of polymethyl methacrylate-polybutadiene core-shell particles, core-shell rubber particles (CSR) and organic silicon core-shell particles; the hyperbranched unsaturated polyester can be one of hyperbranched unsaturated resin or hyperbranched vinyl ester resin; the spherical silicon micro powder is an industrial product, 800-2000 mesh, and the nano calcium carbonate is an industrial product; the dispersant is
5215. One or more of special dispersant 3219, BYK-P104S and BYK-142 for the composite material; the curing agent is one or more of benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, 2, 4-dichlorobenzoyl peroxide and lauroyl peroxide; the blender is one or more of dibutyl phthalate, dimethyl phthalate, pentadecane, isododecane and ethyl acetate, and the inorganic filler is one or more of calcium carbonate, active barium sulfate, active calcium carbonate, double-flying powder, silicon dioxide and aluminum hydroxide; the stabilizer in the component B is selected from calcium stearate, lead stearate, cadmium stearate and zinc stearateOne or more of; the accelerant is one or more of N, N-dimethylaniline, N-diethylaniline, N-dimethyl-p-toluidine, N-methyl-N-hydroxyethyl aniline, N-methyl-N-hydroxyethyl-p-toluidine, N-methyl-N-hydroxypropyl-p-toluidine, N-dihydroxyethyl aniline and homologues thereof; the polymerization inhibitor is one or more of hydroquinone, 2, 5-di-tert-butyl hydroquinone, methyl hydroquinone, p-benzoquinone and 4-tert-butyl catechol.
The bisphenol A type epoxy vinyl resin in the component A has an epoxy structure, and can endow the invention with excellent mechanical property, heat resistance and chemical resistance. In addition, the dicyclopentadiene modified unsaturated polyester resin has the characteristics of low viscosity and high reaction activity, and the usage amount of a cross-linking agent is reduced. The hyperbranched unsaturated polyester is used as a cross-linking agent and a diluent in a system, the flexible molecular chain segment of the hyperbranched unsaturated polyester promotes the curing rate of the adhesive while reducing the viscosity of the system, and the curing system has certain cross-linking network density, so that various mechanical properties after curing are improved. In addition, because the low-boiling point active diluent and styrene in the adhesive system are removed, the risk of back net cementing ice (columnar crystals formed by the volatilization and self polymerization of the styrene) is greatly reduced, and the content of total Volatile Organic Compounds (VOCs) in the adhesive is greatly reduced by adding the hyperbranched unsaturated polyester. The three components are mutually matched to endow the back mesh adhesive with more excellent impact resistance, corrosion resistance, heat resistance, weather resistance, excellent room temperature curing rate and better environmental protection effect.
According to the toughening type environment-friendly back mesh adhesive, the core-shell particle toughening agent and the nanoparticle filler composition are selected as the reinforcing agent of the component A, and the core-shell particles are combined with the vinyl resin and are mutually linked to form a sea-island structure and a cavity effect to play an energy storage role; the nanofiller disperses the residual stress in the cured system. The adhesive and the preparation method greatly improve the mechanical property of the solidified back-mesh adhesive, enhance the adhesive force of the adhesive to the stone back plate and the mesh yarns, and increase the adhesive force and the adhesive strength of the adhesive layer to the main material when the back-mesh veneer stone is paved and adhered on the cement mortar surface, particularly the impact toughness is obviously improved.
The toughening type environment-friendly back mesh adhesive provided by the invention adopts hyperbranched unsaturated polyester, and simultaneously is matched with spherical silicon micro powder for synergistic effect, so that the purposes of reducing the viscosity of a back mesh colloid system and improving the wettability are achieved.
The hyperbranched unsaturated polyester has a typical hyperbranched structure, has a three-dimensional network structure, has the characteristics of low viscosity, high solubility, difficult crystallization, difficult winding among molecules, a large number of terminal functional groups and extremely strong chemical reaction activity, can effectively reduce the use amount of organic solvents in thermosetting resin and play a role of crosslinking monomers, and the flexible structure of the hyperbranched unsaturated polyester can also improve the impact toughness of materials after crosslinking and curing. The spherical silicon micro powder has good surface fluidity, is uniformly dispersed after being stirred with resin, requires small addition amount of the resin, has the best fluidity and high filling amount of the powder. The two materials are matched for use, so that the impact toughness of the cured back mesh adhesive can be effectively improved, the effect of a styrene crosslinking monomer diluent in unsaturated resin can be completely replaced, toxic, harmful and volatile styrene in a back mesh adhesive system is removed, and the purposes of protecting the environment and protecting the body health of a user are achieved. On the other hand, the spherical silica micropowder has uniform shape and good surface fluidity, has low influence on the wettability of resin when used as a filler, and can ensure that the back mesh adhesive can fully permeate into holes and gaps of the stone and the back mesh, thereby improving the bonding effect.
The following are examples:
example 1-example 15
Examples 1-15 (abbreviated as examples 1-15 in the tables) are all preferred examples of the present invention), the components of the component A are listed in Table 1, the components of the component B are listed in Table 2 (the data of the raw materials in tables 1 and 2 are calculated according to the weight portion ratio):
TABLE 1A Components
TABLE 1A Components (continuation)
TABLE 2B Components
TABLE 2B Components (continuation)
Preparing the back mesh glue according to the mixture ratio in the tables 1 and 2, stirring the component B for 1-2 hours by adopting a kneading kettle, and mixing the components in a weight ratio of 100: 5 to 10 percent of the total weight of the mixture of the component A and the component B is fully mixed, and the curing agent accounts for 0.5 to 3.5 percent of the total weight of the mixture of the component A and the component B.
The mechanical property test of the condensate is carried out by referring to a test method of building material industry standard JC/T989-2006 of the people's republic of China, wherein the test method comprises the steps of flexural modulus of elasticity, impact toughness, compression-shear bonding strength (standard, soaking, heat treatment and freeze-thaw cycle); and measured for pot life (i.e., gel time) and solids at 25 deg.C
The shrinkage ratios are shown in Table 3.
TABLE 3 mechanical Properties and pot life of the adhesive
As can be seen from table 3, the back mesh adhesive of the present invention has the advantages of low viscosity, good permeability, moderate rheological property, low content of total Volatile Organic Compounds (VOCs), etc., and simultaneously has very excellent anti-shrinkage performance, water resistance, weather resistance, mechanical strength, especially impact resistance.
Comparative examples 1 to 3
The gel time and shrinkage of the environment-friendly back mesh adhesive of example 1 of the present invention were compared with those of commercially available cement mortar (comparative example 1), commercially available unsaturated polyester resin back mesh adhesive (comparative example 2) and commercially available epoxy resin back mesh adhesive (comparative example 3), and the comparison results are shown in table 4.
In table 4, the component a in example 1 of the present invention includes the following raw materials in parts by weight: 50 parts of dicyclopentadiene modified unsaturated polyester resin, 40 parts of bisphenol A epoxy vinyl resin, 40 parts of hyperbranched unsaturated resin HyPer U10213.5 parts, BYK-P104S 1 parts, 0.04 part of hydroquinone, 0.5 part of N, N-dimethylaniline, 10 parts of polymethyl methacrylate-polybutadiene core-shell particles, 40 parts of 1250-mesh spherical silica powder and 20 parts of nano calcium carbonate; the component B comprises the following raw materials in parts by weight: 35 parts of benzoyl peroxide, 45 parts of dibutyl phthalate, 7 parts of calcium stearate, 10 parts of activated calcium carbonate, 10 parts of silicon dioxide and 10 parts of boomerang powder, wherein the component A and the component B are mixed according to the weight ratio of 100:7, the determination of the total volume shrinkage of ISO 3521-.
TABLE 425 deg.C gel time and shrinkage comparative table
| Species of | Initial setting time | Complete curing | Shrinkage rate |
| Example 1 | 5’24” | 7’33” | 2.4％ |
| Comparative example 1 | 45’21” | 20h | 7.5％ |
| Comparative example 2 | 5’16” | 7’18” | 7.5％ |
| Comparative example 3 | 32’38” | 2h | 4％ |
Example 1: preferred embodiment of the invention example 1;
comparative example 1: commercial cement cements;
comparative example 2: commercially available unsaturated polyester resin back mesh glue;
comparative example 3: epoxy resin back mesh glue is commercially available.
As shown in table 4, in the preferred example 1, the curing time at 25 ℃ was comparable to that of the commercially available unsaturated polyester back-mesh adhesive, and the shrinkage was smaller than that of the commercially available cement paste and epoxy resin back-mesh adhesive.
Comparative examples 4 to 8
Comparative examples 4 to 8 are comparisons of total volatile organic content of back-mesh adhesives, commercially available unsaturated polyester resin back-mesh adhesives, and commercially available epoxy resin back-mesh adhesives obtained under the same component B and different component a resin compounding conditions, with the environment-friendly back-mesh adhesive of example 2 of the present invention.
The component A comprises the following raw materials in parts by weight: 100 parts of matrix resin, 1 part of composite material special dispersant 3219, 0.03 part of hydroquinone, 0.5 part of N, N-dimethyl-p-toluidine, 10 parts of organic silicon core-shell particles, 30 parts of 1250-mesh spherical silica powder and 20 parts of nano calcium carbonate;
the component B comprises the following raw materials in parts by weight: 40 parts of benzoyl peroxide, 35 parts of dibutyl phthalate, 7 parts of calcium stearate and 30 parts of aluminum hydroxide.
Mixing and uniformly stirring the component A and the component B according to the weight ratio of 100:7, and completely curing, and testing the impact toughness and the compression-shear bonding strength (standard, soaking, heat treatment and freeze-thaw cycle) of a cured product of the component A by referring to a test method of a building material industry standard JC/T989-2006 of the people's republic of China; the total Volatile Organic Compounds (VOCs) were calculated according to GB18583-2008 "Limit of harmful substance in adhesive for interior decoration Material", and the results are shown in Table 5.
TABLE 5 comparison of Properties of different component resins
Comparative example 4: 85 parts of bisphenol A type epoxy vinyl resin and 15 parts of hyperbranched unsaturated polyester;
comparative example 5: 85 parts of dicyclopentadiene modified unsaturated polyester resin and 15 parts of hyperbranched unsaturated polyester;
comparative example 6: 55 parts of dicyclopentadiene modified unsaturated polyester resin, 30 parts of bisphenol A epoxy vinyl resin and 15 parts of styrene;
embodiment 2 of the present invention: 55 parts of dicyclopentadiene modified unsaturated polyester resin, 30 parts of bisphenol A epoxy vinyl resin and 15 parts of hyperbranched unsaturated polyester;
comparative example 7: commercially available unsaturated polyester resin back mesh glue;
comparative example 8: epoxy resin back mesh glue is commercially available.
As can be seen from the experimental data in Table 5, the back mesh adhesive obtained by blending three resins in example 2 has the characteristics of excellent impact resistance and good heat and aging resistance, so that the back mesh adhesive is superior to back mesh adhesives prepared from other resins in various mechanical properties (comparative examples 4-6) and also superior to commercially available unsaturated polyester resin back mesh adhesives (comparative example 7) and epoxy resin back mesh adhesives (comparative example 8). The total volatile organic content of the back mesh adhesive after the unsaturated polyester is added is far lower than that of the back mesh adhesive added with styrene and commercially available unsaturated polyester resin back mesh adhesive and also lower than that of commercially available epoxy resin back mesh adhesive.
Comparative examples 9 to 11, examples 16 to 17
Comparative examples 9 to 11, and examples 16 to 17 are mechanical property tests and comparisons of cured products of the environment-friendly back mesh adhesive under the condition that the core-shell particle toughening agent is added under different conditions, with other components unchanged.
The component A comprises the following raw materials in parts by weight: 55 parts of dicyclopentadiene modified unsaturated polyester resin, 30 parts of bisphenol A epoxy vinyl resin, 10215 parts of hyperbranched unsaturated resin HyPer U, BYK-1421 parts of methyl hydroquinone, 0.03 part of N, N-dimethylaniline and 40 parts of 1250-mesh spherical silicon micro powder, and then adding a certain amount of core-shell particle toughening agent and a certain amount of nano calcium carbonate; the component B comprises the following raw materials in parts by weight: 20 parts of benzoyl peroxide, 20 parts of 2, 4-dichloro benzoyl peroxide, 35 parts of dibutyl phthalate, 7 parts of cadmium stearate, 10 parts of calcium carbonate, 10 parts of active barium sulfate, 10 parts of calcium carbonate and 10 parts of aluminum hydroxide. The component A and the component B are mixed and stirred uniformly according to the weight ratio of 100:7, and the mechanical property test result of the condensate is shown in the following table 6 by referring to the test method of JC/T989-2006.
TABLE 6 mechanical properties of the back mesh glue with core-shell particle toughening agent and nano calcium carbonate added
Remarking:
comparative example 9: blank comparison sample;
comparative example 10: 10 parts of polymethyl methacrylate-polybutadiene core-shell particles;
comparative example 11: 20 parts of nano calcium carbonate;
example 3: 20 parts of nano calcium carbonate and 10 parts of polymethyl methacrylate-polybutadiene core-shell particles;
example 16: 20 parts of nano calcium carbonate, 5 parts of organic silicon core-shell particles and 5 parts of core-shell rubber particles;
example 17: 20 parts of nano calcium carbonate, 3 parts of polymethyl methacrylate-polybutadiene core-shell particles and organic silicon core-shell particles
3 parts of core-shell rubber particles and 4 parts of core-shell rubber particles.
As shown in Table 6, in the examples 3, 16 and 17 of the present invention, various mechanical strengths, especially impact toughness, were greatly improved after adding different types of core-shell particle toughening agents and nano calcium carbonate; and the reinforcing effect of the back mesh adhesive by adding the core-shell particle toughening agent and the nano calcium carbonate is obviously better than that by adding the single-component filler.
Comparative examples 12 to 13
Comparative examples 12-13 are comparisons of the viscosity of different classes of cross-linking monomer diluents and silica powder back web adhesives with the other components unchanged with example 4 of the present invention.
The component A comprises the following raw materials in parts by weight: 60 parts of dicyclopentadiene modified unsaturated polyester resin, 25 parts of bisphenol A epoxy vinyl resin, 15 parts of crosslinking monomer diluent, 0.5 part of BYK-P104S 1, 0.03 part of 4-tert-butyl catechol, 0.5 part of N-methyl-N-hydroxyethyl P-toluidine, 5 parts of core-shell rubber particles, 40 parts of silicon powder and 25 parts of nano calcium carbonate; the component B comprises the following raw materials in parts by weight: 45 parts of lauroyl peroxide, 40 parts of dibutyl phthalate, 7 parts of calcium stearate and 30 parts of aluminum hydroxide.
According to GB/T2794-:
TABLE 7 viscosity of silica powder back web with addition of different classes of crosslinking monomer diluents
| Example numbering | Comparative example 12 | Comparative example 13 | Example 4 |
| Viscosity (mPa. s) at 60r/min | 2170 | 3321 | 1922 |
| Viscosity (mPa. s) at 6r/min | 5124 | 7376 | 3365 |
Remarking:
comparative example 12 styrene 15 parts, 1250 mesh silica powder 40 parts;
comparative example 13 hyperbranched vinyl ester resin HyPer HPS 15 parts, silica powder of 1250 mesh 40 parts;
example 4 hyperbranched vinyl ester resin HyPer HPS 15 parts, 1250 mesh spherical silica micropowder 40 parts;
as shown in table 7 above, the viscosity of the back-mesh adhesive added with the spherical silica powder is obviously lower than that of the common silica powder, and the viscosity of the added hyperbranched vinyl ester resin HyPer HPS and 1250-mesh spherical silica powder is lower than that of the added styrene and 1250-mesh silica powder.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The toughening type back mesh adhesive is characterized by comprising a component A, wherein the component A comprises the following components in parts by weight: 45-65 parts of dicyclopentadiene modified unsaturated polyester resin, 25-40 parts of bisphenol A epoxy vinyl resin, 10-15 parts of hyperbranched unsaturated polyester, 1-2.5 parts of dispersing agent, 5-15 parts of core-shell particle toughening agent, 25-40 parts of spherical silicon micro powder, 15-25 parts of nano calcium carbonate, 0.2-0.8 part of accelerator and 0.02-0.08 part of polymerization inhibitor;
the back mesh adhesive also comprises a component B, wherein the component B comprises the following components in parts by weight: 10-70 parts of curing agent, 30-40 parts of blending agent, 30-50 parts of inorganic filler and 3-10 parts of stabilizing agent.
2. The toughening type back mesh adhesive according to claim 1, wherein the weight ratio of the component A to the component B meets the following conditions: the A component and the B component are mixed to ensure that the curing agent accounts for 0.5-3.5% of the total weight of the mixture.
3. The toughening-type back mesh adhesive of claim 1, wherein the core-shell particle toughening agent is one or more of polymethyl methacrylate-polybutadiene core-shell particles, core-shell rubber particles and silicone core-shell particles.
4. The toughening type back mesh adhesive of claim 1, wherein the spherical silica micro powder has a mesh size of 800-2000 mesh.
5. The toughened back mesh adhesive as claimed in claim 1, wherein said curing agent is selected from one or more of benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, 2, 4-dichlorobenzoyl peroxide and lauroyl peroxide.
6. The toughening type back mesh adhesive according to claim 1, wherein the stabilizer is one or more selected from calcium stearate, cadmium stearate, zinc stearate, and lead stearate.
7. The preparation method of the toughening type back mesh adhesive according to any one of claims 1 to 6, which comprises the following steps:
(1) preparation of component A: adding dicyclopentadiene modified unsaturated polyester resin, bisphenol A epoxy vinyl resin and hyperbranched unsaturated polyester into a reaction kettle, adding a dispersing agent, stirring for 30-45 minutes under a heating condition, then adding pretreated spherical silica micropowder, nano calcium carbonate, an accelerator, a polymerization inhibitor and a core-shell particle flexibilizer, after adding materials, heating to 60-80 ℃, vacuumizing to-0.1 Mpa, keeping vacuum high-speed stirring for 1500-2000 r/min, keeping the temperature for ultrasonic dispersion for 45 minutes, then cooling to 20-40 ℃, stopping stirring, discharging, filtering by a 100-mesh filter screen with 200 meshes, packaging and sealing to obtain a component A;
(2) preparation of the component B: and adding the curing agent, the blending agent, the stabilizer and the inorganic filler into the reaction kneading kettle in sequence under the stirring condition, continuously stirring for 1-2 hours after the materials are added, stopping stirring, discharging, packaging and sealing to obtain the component B.
8. The use of the toughening-type back net glue according to any one of claims 1 to 6, wherein the A component and the B component are mixed when in use, and the weight of the curing agent accounts for 0.5 to 3.5 percent of the total weight of the mixture of the A component and the B component after the A component and the B component are mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710481453.4A CN107090264B (en) | 2017-06-22 | 2017-06-22 | Toughened environment-friendly back mesh adhesive as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710481453.4A CN107090264B (en) | 2017-06-22 | 2017-06-22 | Toughened environment-friendly back mesh adhesive as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107090264A CN107090264A (en) | 2017-08-25 |
| CN107090264B true CN107090264B (en) | 2020-05-15 |
Family
ID=59640827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710481453.4A Active CN107090264B (en) | 2017-06-22 | 2017-06-22 | Toughened environment-friendly back mesh adhesive as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107090264B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107619654A (en) * | 2017-10-24 | 2018-01-23 | 广东晨宝复合材料有限公司 | Quick-dry type natural stone back of the body unsaturated polyester resin and preparation method thereof |
| CN108410408B (en) * | 2018-03-19 | 2021-01-15 | 江苏大力士投资有限公司 | High-toughness marble adhesive and preparation method thereof |
| CN109181256B (en) * | 2018-08-28 | 2021-01-15 | 江苏澳盛复合材料科技有限公司 | Unsaturated resin composition and preparation method thereof |
| CN112126395B (en) * | 2020-09-21 | 2022-01-11 | 烟台大学 | Thixotropic ultraviolet curing adhesive |
| CN112521896B (en) * | 2020-11-12 | 2022-03-22 | 武汉市科达云石护理材料有限公司 | Environment-friendly stone back bar adhesive and preparation method thereof |
| CN112521898B (en) * | 2020-11-12 | 2022-03-22 | 武汉市科达云石护理材料有限公司 | Stone back bar adhesive and preparation method thereof |
| CN113943473B (en) * | 2021-11-23 | 2023-11-28 | 广东盈骅新材料科技有限公司 | High-toughness epoxy resin composition and preparation process thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735759A (en) * | 2009-12-10 | 2010-06-16 | 江苏大力士投资有限公司 | High-performance marble glue and preparation method thereof |
| JP6224943B2 (en) * | 2013-07-17 | 2017-11-01 | イズミ物産株式会社 | One-component solvent-free room temperature curable organosiloxane silicone resin adhesive and method for producing the same |
| CN105441004B (en) * | 2015-12-01 | 2018-06-19 | 武汉市科达云石护理材料有限公司 | A kind of flame-retardant ethylene fundamental mode anchoring adhesive |
-
2017
- 2017-06-22 CN CN201710481453.4A patent/CN107090264B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107090264A (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107090264B (en) | Toughened environment-friendly back mesh adhesive as well as preparation method and application thereof | |
| US5162060A (en) | Polymer-modified cements with improved chemical resistance | |
| AU644392B2 (en) | Water-based composites with superior cure in thick films, and chemical and shock resistance | |
| KR101083584B1 (en) | A red and green dry adhesive, a method producing the same | |
| EP1048676B2 (en) | Polymer compositions | |
| CN109385242B (en) | Epoxy joint mixture and preparation method thereof | |
| US10259749B2 (en) | Premixed hybrid grout | |
| KR101859736B1 (en) | Adhesive compositions for polishing tile and construction method using the same | |
| CN114890753B (en) | Mining thin-spraying flexible supporting material | |
| CN106497473A (en) | A kind of environment protection type single-component vitrified brick gum and preparation method thereof | |
| CN105950069A (en) | Rubber-modified UV curable adhesive | |
| CN106753094B (en) | A kind of aqueous high-strength nail-free glue | |
| KR101805992B1 (en) | Rapid drying paint composition for reparing crack using methyl methacrylate resin | |
| CN111004600A (en) | Novel glue for stone compounding | |
| CN111039587B (en) | Reinforcing agent suitable for cement-based tile adhesive and preparation method thereof | |
| KR100929612B1 (en) | One-component aqueous adhesive composition and preparation method thereof | |
| CN109231939B (en) | Single-component paste joint mixture and preparation method thereof | |
| KR20030020020A (en) | A composite of adhesives for a hot-floored plate of the polymer cement system | |
| CN117025145A (en) | Epoxy resin dry-hanging adhesive and preparation method thereof | |
| CN108383428A (en) | Modified vinyl mortar and preparation method thereof under a kind of wet environment | |
| CN117820998A (en) | Epoxy adhesive and preparation method and application thereof | |
| CN112961612A (en) | High-strength high-weather-resistance rock plate adhesive and preparation method thereof | |
| CN118043290A (en) | Brick powder as filler in multicomponent systems for chemical fastening | |
| KR20210041414A (en) | Artificial marble composition | |
| JPH0463891B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230828 Address after: No. 6 Danjin Road, Industrial Concentration Zone, Baita Town, Jintan District, Changzhou City, Jiangsu Province, 213299 Patentee after: Jiangsu Hercules Marble Care Materials Co.,Ltd. Address before: No. 26 Jinhai Industrial Park, Jinshan Avenue, Dongxihu District, Wuhan City, Hubei Province, 430040 Patentee before: WUHAN KEDA MARBLE PROTECTIVE MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |