CN109503764B - Glass fiber mesh fabric latex and preparation method thereof - Google Patents
Glass fiber mesh fabric latex and preparation method thereof Download PDFInfo
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- CN109503764B CN109503764B CN201811252149.3A CN201811252149A CN109503764B CN 109503764 B CN109503764 B CN 109503764B CN 201811252149 A CN201811252149 A CN 201811252149A CN 109503764 B CN109503764 B CN 109503764B
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- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract
The invention relates to the field of adhesives, and discloses a glass fiber mesh fabric latex and a preparation method thereof, which solve the problems of low bonding strength and easy peeling of the existing latex coating and glass fiber.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to glass fiber mesh fabric latex and a preparation method thereof.
Background
The glass fiber mesh fabric is a latex coating formed by soaking a glass fiber woven fabric serving as a base material in a high-molecular polymer emulsion. Therefore, the high-strength heat-insulating waterproof mortar has good alkali resistance, flexibility and high tensile resistance in the warp and weft directions, and can be widely used for heat insulation, water resistance, crack resistance and the like of inner and outer walls of buildings.
The flexibility of the glass fiber mesh cloth is influenced by the latex coating formed by soaking the surface of the glass fiber mesh cloth, when the glass transition temperature of a high polymer in the coating is lower, the high polymer has good fluidity, the coating has good extensibility when being stressed and stretched, and the resistance suffered by the glass fiber mesh cloth when being bent is reduced. When the glass transition temperature of the high molecular polymer in the coating is lower, the high molecular polymer has poor flowability and strong brittleness, so that the coating is easy to break when being stressed and stretched, and the glass fiber mesh cloth is prevented from bending. Therefore, the polymer composition in the existing high molecular polymer emulsion generally selects the polymer with lower glass transition temperature, and the existing latex meets the requirements of the styrene-butadiene latex and partially modified styrene-butadiene latex.
The method has the disadvantages that the glass transition temperature of the high molecular polymer in the coating is low, so that the fluidity is good, the bonding strength of the coating and the glass fiber is reduced, when the glass fiber mesh cloth is unfolded from a rolled state or is contacted and adhered with a wall surface or the surface of other objects due to wrong operation, the coating is easy to peel off from the glass fiber mesh in the separation process of the glass fiber mesh cloth, the glass fiber is exposed, so that the glass fiber is aged, and the improvement is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the glass fiber mesh fabric latex, which improves the adhesion and the bonding strength between a coating and the surface of glass fiber, improves the anti-blocking property of the coating, and further reduces the possibility that the coating is peeled off from the glass fiber.
The technical purpose of the invention is realized by the following technical scheme:
the glass fiber mesh fabric latex is prepared from the following raw materials in parts by mass through emulsion polymerization:
15-20 parts of seed latex,
130 portions and 150 portions of oil-phase liquid,
120-140 portions of water-phase liquid,
6-10 parts of an initiator solution,
100 portions and 120 portions of soft water,
the seed latex is prepared by mixing the following raw materials in parts by mass: 15-35 parts of styrene, 50-65 parts of butadiene, 10-15 parts of emulsifier, 2-3.5 parts of first initiator and 300 parts of water 250-;
the oil phase liquid is prepared by mixing the following raw materials in parts by weight: 70-90 parts of styrene, 40-55 parts of butadiene, 1-3 parts of a chain transfer agent and 5-10 parts of siloxane;
the water-phase liquid comprises the following raw materials in parts by weight: 3-8 parts of a cross-linking agent and 150 parts of water 130-;
the initiator solution comprises the following raw materials in parts by mass: 7-12 parts of a second initiator and 90-130 parts of water.
By adopting the technical scheme, the latex particles form a core-shell structure, wherein the butadiene in the core-structure polymeric raw material accounts for a larger proportion than the styrene, the butadiene in the shell-structure polymeric raw material accounts for a smaller proportion than the styrene, the glass transition temperature of the core structure is lower than that of the shell structure, and the fluidity of the core structure is higher than that of the shell structure, so that the latex particles can deform, and after the coating is cured, when the glass fiber gridding cloth is bent, the coating is easier to deform along with the glass fiber gridding cloth, and the flexibility of the glass fiber gridding cloth is improved;
meanwhile, the brittleness of the shell structure is greater than that of the core structure, and after the surface of the coating is cured, the viscosity of the shell structure of the latex particles on the surface of the coating is reduced, the adhesion of the two coatings after being attached is reduced, and the possibility of the coating peeling off from the glass fiber is reduced;
siloxane is mixed in the shell structure, and a silicon-oxygen bond in the siloxane can react with free hydroxyl on the surface of the glass fiber, so that the adhesive force and the bonding strength between the coating and the surface of the glass fiber are improved, the anti-blocking property of the coating is improved, and the possibility of peeling the coating from the glass fiber is further reduced;
and the siloxane also reacts with the alkaline metal oxide on the surface of the glass fiber and is attached to the surface of the alkaline metal oxide, so that the alkaline metal oxide is prevented from reacting with water to generate alkali liquor, and the mechanical property and the ageing resistance of the glass fiber are improved.
Preferably, the siloxane is an alkenyl siloxane.
By adopting the technical scheme, the siloxane can be polymerized with a butadiene monomer and a styrene monomer, and the siloxane is grafted into a butadiene-styrene polymerization system, so that the siloxane is prevented from being separated out from latex or a coating, and the compatibility of the siloxane in the butadiene-styrene polymerization system is enhanced; the siloxane which is connected into the butadiene-styrene polymerization system can be crosslinked, the crosslinking degree in the butadiene-styrene polymerization system is improved, the bonding strength of the coating is improved, the siloxane is grafted into the butadiene-styrene polymerization system and then is combined with the surface of the glass fiber, the adhesive force and the bonding strength between the coating and the surface of the glass fiber are further improved, and the possibility that the coating is peeled off from the glass fiber is further reduced.
Preferably, the siloxane is a vinyl siloxane.
By adopting the technical scheme, the silicon atom with the alkoxy group is connected to the carbon atom of the vinyl, the vinyl siloxane is grafted into the butadiene-styrene polymerization system, the vinyl carried by the vinyl siloxane is prevented from continuing to perform polyaddition under the influence of steric hindrance, the chain length and the molecular weight of the butadiene-styrene polymerization system are limited, the adhesive strength of the coating is improved, the grafting amount of the vinyl siloxane to the butadiene-styrene polymerization system is increased, the adhesive force and the adhesive strength between the coating and the glass fiber are enhanced through the siloxane, and the possibility that the coating is peeled off from the glass fiber is further reduced.
Preferably, the aqueous phase liquid comprises 25-35 parts of alkenyl carboxylic acid, and the siloxane is epoxyalkyl siloxane.
By adopting the technical scheme, the alkenyl carboxylic acid can be polymerized with the butadiene monomer and the styrene monomer to form an alkenyl carboxylic acid-butadiene-styrene polymerization system, so that the viscosity of the latex is reduced, and the blocking resistance of the coating is improved;
the epoxyalkyl siloxane reacts with carboxyl in the alkenyl carboxylic acid-butadiene-styrene polymerization system to form ester bonds, so that the epoxyalkyl siloxane is grafted into the alkenyl carboxylic acid-butadiene-styrene polymerization system, and the water resistance of the coating is improved;
the silicon-oxygen bond in the siloxane grafted into the polymerization system is less influenced by the steric hindrance of the polymerization chain, so that the siloxane grafted into the polymerization system is more easily crosslinked with the siloxane on other polymerization chains, the crosslinking degree in the polymerization system of butadiene-styrene is improved, and the bonding strength of a coating is improved;
the siloxane is grafted into a polymerization system and then is combined with the surface of the glass fiber, so that the adhesive force and the bonding strength of the coating and the surface of the glass fiber are further improved, and the possibility of the coating peeling off from the glass fiber is further reduced.
Preferably, the alkenyl carboxylic acid is one or two of acrylic acid, itaconic acid and methacrylic acid.
By adopting the technical scheme, the crosslinking degree of the emulsion is improved, so that the bonding strength is improved, and the water resistance is improved.
Preferably, the crosslinking agent is N-methylolacrylamide and N-alkyl octyl methacrylamide, and the mass ratio of the N-methylolacrylamide to the N-alkyl octyl methacrylamide is 1: 1-1.5.
Preferably, the latex raw material also comprises 15-20 parts of consistency adjusting liquid; the consistency regulating liquid is prepared by mixing the following raw materials in parts by weight: 8-10 parts of DOPO and 25-30 parts of ethanol.
By adopting the technical scheme, the DOPO has P-H bonds, can react with carbon-carbon double bonds, reduces the saturation, blocks the polymerization process, adjusts the molecular weight of a polymerization system, so as to adjust the viscosity of latex and the viscosity of a coating, improve the anti-adhesion property of the coating and reduce the possibility that the coating peels off from glass fibers; meanwhile, DOPO grafted into the polymer is stably dispersed in the latex, and the flame resistance of the coating is improved.
In view of the defects in the prior art, another object of the present invention is to provide a method for preparing the glass fiber mesh cloth latex, such that the monomer concentration and the siloxane concentration on the surface of the latex particle are high, and the possibility of the coating peeling off from the glass fiber is further reduced.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of glass fiber mesh cloth latex comprises the following steps,
s1: vacuumizing a polymerization kettle, adding 15-35 parts of styrene, 50-65 parts of butadiene, 10-15 parts of emulsifier and 300 parts of water 250-containing material at one time, stirring, heating to 40-60 ℃, adding 2-3.5 parts of first initiator, keeping the temperature, continuously stirring for reaction for 10-25 hours, and cooling to below 30 ℃ after the reaction reaches more than 98% of conversion rate to obtain seed latex;
s2: uniformly mixing 70-90 parts of styrene and 1-3 parts of chain transfer agent, adding 40-55 parts of butadiene, uniformly mixing, adding 5-10 parts of siloxane, and uniformly mixing to obtain an oil phase liquid;
s3: uniformly mixing 3-8 parts of cross-linking agent, 320 parts of water 250-and other aqueous phase liquid raw materials to obtain aqueous phase liquid;
s4: uniformly mixing 7-12 parts of a second initiator and 90-130 parts of water to obtain an initiator solution;
s5: adding 15-20 parts of seed latex and 150 parts of water 130-containing organic solvent into another polymerization kettle, uniformly stirring, heating to 75 ℃ after uniform mixing, adding 140 parts of water-phase liquid and 150 parts of oil-phase liquid 130-containing organic solvent, simultaneously dropwise adding 6-10 parts of initiator solution, wherein the dropwise adding completion time is 1-2h, after the dropwise adding, carrying out heat preservation reaction for 2-3 h, and controlling the temperature to be 80-90 ℃;
s6: and gradually cooling the liquid in the polymerization kettle to below 30 ℃ to obtain the product latex.
By adopting the technical scheme, the aqueous phase liquid and the oil phase liquid are added at one time, and polymerization is initiated under the action of the initiator, so that the monomer concentration and the siloxane concentration on the surface of the emulsion particle are high, the siloxane is favorably combined with the glass fiber, the adhesive force and the adhesive strength between the coating and the surface of the glass fiber are improved, and the possibility that the coating is peeled off from the glass fiber is further reduced.
In view of the defects of the prior art, another object of the present invention is to provide a method for preparing the glass fiber mesh cloth latex, which can improve the anti-blocking property of the coating and reduce the possibility of the coating peeling off from the glass fiber.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of glass fiber mesh cloth latex comprises the following steps,
s1: vacuumizing a polymerization kettle, adding 15-35 parts of styrene, 50-65 parts of butadiene, 10-15 parts of emulsifier and 300 parts of water 250-containing material at one time, stirring, heating to 40-60 ℃, adding 2-3.5 parts of first initiator, keeping the temperature, continuously stirring for reaction for 10-25 hours, and cooling to below 30 ℃ after the reaction reaches more than 98% of conversion rate to obtain seed latex;
s2: uniformly mixing 70-90 parts of styrene and 1-3 parts of chain transfer agent, adding 40-55 parts of butadiene, uniformly mixing, adding 5-10 parts of siloxane, and uniformly mixing to obtain an oil phase liquid;
s3: uniformly mixing 3-8 parts of cross-linking agent, 320 parts of water 250-and other aqueous phase liquid raw materials to obtain aqueous phase liquid;
s4: uniformly mixing 7-12 parts of a second initiator and 90-130 parts of water to obtain an initiator solution;
s5: adding 15-20 parts of seed latex and 150 parts of water 130-containing organic solvent into another polymerization kettle, stirring, uniformly mixing, heating to 75 ℃, adding 140 parts of water-phase liquid and 150 parts of oil-phase liquid, simultaneously dropwise adding 6-10 parts of initiator solution, wherein the dropwise adding completion time is 1-2h, after the dropwise adding, carrying out heat preservation reaction for 1-2h, and controlling the temperature to be 80-90 ℃; adding 15-20 parts of dropwise consistency regulating liquid for 1-2h, controlling the temperature at 80-90 ℃ after dropwise addition, keeping the temperature for reaction for 1-2h, and distilling to remove ethanol after the reaction is finished;
s6: after ethanol is removed, the liquid in the polymerization kettle is gradually cooled to below 30 ℃ to obtain the product latex.
By adopting the technical scheme, when the consistency regulating liquid is dripped into the liquid in the polymerization kettle, the consistency regulating liquid is rapidly dispersed along with stirring, DOPO dissolved in ethanol is dispersed along with the ethanol in the liquid in the polymerization kettle, the dispersion is more uniform, the DOPO grafting reaction is facilitated, on the other hand, the DOPO is removed along with the distillation of the ethanol, the ethanol vapor carries and removes residual polymer monomers and micromolecule byproducts in latex, the anti-blocking property of the coating is improved, and the possibility that the coating is peeled off from the glass fiber is reduced.
In conclusion, the invention has the following beneficial effects:
1. the latex particles form a core-shell structure, the brittleness of the shell structure is greater than that of the core structure, and after the surface of the coating is cured, the viscosity of the shell structure of the latex particles on the surface of the coating is reduced, the adhesion of the two coatings after being attached is reduced, and the possibility of the coating peeling off from the glass fiber is reduced;
2. the siloxane is mixed in the shell structure and is combined with the surface of the glass fiber, so that the adhesive force and the adhesive strength of the coating and the surface of the glass fiber are improved, the anti-blocking property of the coating is improved, the possibility of peeling the coating from the glass fiber is reduced, and the mechanical property and the anti-aging property of the glass fiber are improved;
3. the siloxane is grafted into a polymerization system of butadiene-styrene, so that the compatibility of the siloxane in the polymerization system is enhanced; siloxane which is connected into a polymerization system is combined with the surface of the glass fiber, so that the adhesive force and the adhesive strength between the coating and the surface of the glass fiber can be further improved, and the possibility of peeling off the coating from the glass fiber is reduced; meanwhile, the siloxane which is connected into the polymerization system can be crosslinked, so that the crosslinking degree in the polymerization system is improved, and the bonding strength of the coating is improved;
4. the siloxane is vinyl silane, and after the vinyl siloxane is grafted into a butadiene-styrene polymerization system, polymerization is affected by steric hindrance, the chain length and the molecular weight of the polymerization system are limited, the bonding strength of the coating and the grafting amount of the vinyl siloxane are improved, and the possibility that the coating peels off from the glass fiber is reduced;
5. the water phase liquid comprises alkenyl carboxylic acid, the siloxane is epoxyalkyl siloxane, and the epoxyalkyl siloxane is grafted into a polymerization system, so that the water resistance of the coating is improved; meanwhile, the grafted epoxyalkyl siloxane is easy to crosslink with siloxane on other polymer chains, so that the crosslinking degree in a polymerization system is improved, and the bonding strength of a coating is improved;
DOPO can react with carbon-carbon double bonds to block the polymerization process, adjust the molecular weight of a polymerization system to adjust the viscosity of latex and the viscosity of a coating, improve the anti-adhesion property of the coating, reduce the possibility that the coating is peeled off from glass fibers, and improve the flame resistance of the coating;
7. when the latex is polymerized in emulsion, the aqueous phase liquid and the oil phase liquid are added at one time for polymerization, so that the monomer concentration and the siloxane concentration on the surface of the latex particle are high, the siloxane is favorably combined with the glass fiber, the adhesive force and the bonding strength between the coating and the surface of the glass fiber are improved, and the possibility that the coating is peeled off from the glass fiber is further reduced;
8. the ethanol in the consistency regulating liquid is removed under distillation, and residual polymer monomers in the latex are carried and removed, so that the blocking resistance of the coating is improved.
Detailed Description
In the first embodiment, the first step is,
a preparation method of glass fiber mesh cloth latex comprises the following steps,
s1: vacuumizing a polymerization kettle, adding 15-35kg of styrene, 50-65kg of butadiene, 10-15kg of emulsifier and 300kg of water 250-;
s2: uniformly mixing 70-90kg of styrene and 1-3kg of chain transfer agent, adding 40-55kg of butadiene, uniformly mixing, adding 5-10kg of siloxane, and uniformly mixing to obtain oil phase liquid;
s3: 3-8kg of cross-linking agent, 250-320kg of water and other raw materials of water phase liquid are uniformly mixed to obtain water phase liquid;
s4: uniformly mixing 7-12kg of second initiator and 90-130kg of water to obtain initiator solution;
s5: adding 15-20kg of seed latex and 150kg of water 130-containing organic solvent into another polymerization kettle, stirring, uniformly mixing, heating to 75 ℃, adding 140kg of water phase liquid 120-containing organic solvent and 150kg of oil phase liquid 130-containing organic solvent, simultaneously dropwise adding 6-10kg of initiator solution, wherein the dropwise adding completion time is 1-2h, after the dropwise adding, carrying out heat preservation reaction for 1-2h, and controlling the temperature to be 80-90 ℃; adding dropwise consistency regulating solution 15-20kg for 1-2h, controlling the temperature at 80-90 deg.C after dropwise addition, reacting for 1-2h, and distilling to remove ethanol after reaction;
s6: after ethanol is removed, the liquid in the polymerization kettle is gradually cooled to below 30 ℃ to obtain the product latex.
Butadiene here refers to 1, 3-butadiene.
The following examples 1A-1I were obtained according to the above procedure, with the following compositional parameters.
(1) Seed latex raw material.
(2) Oil phase liquid feedstock.
(3) An aqueous phase liquid feedstock.
(4) Oil phase liquid feedstock.
(5) Examples 1A to 1I.
Comparative examples 1A-1I were also set up. Comparative examples 1A to 1I corresponding to comparative examples 1A to 1I, the amount of silicone was 0kg and the other components were used in equal amounts, and the latexes corresponding to comparative examples 1A to 1I were obtained according to the procedure described above.
The latexes obtained in examples 1A to 1I and comparative examples 1A to 1I were subjected to a blocking peel test.
Adhesion peel test:
selecting glass fiber mesh cloth and glass fiber cloth, completely immersing the glass fiber mesh cloth and the glass fiber cloth into the test latex, soaking the latex on the surfaces of the glass fiber mesh cloth and the glass fiber cloth, and taking out the glass fiber mesh cloth and the glass fiber cloth to form a coating after the latex is solidified.
The glass fiber mesh cloth with the coating and the glass fiber cloth are cut into three parts, each part is 150 mm-150 mm, the glass fiber mesh cloth with the coating and the glass fiber cloth are aligned, the glass fiber mesh cloth is arranged on the upper part, and the glass fiber cloth is alternately overlapped at the lower part to form a combined sample. The combined sample was aligned between two 150mm by 3mm glass plates and a 5.0kg weight was placed on the glass plate to evenly distribute the pressure and form a sample assembly. The sample assembly was placed in a thermostatted heating cabinet at 30 ℃ and 2 ℃ for 3 h. The sample assembly was removed from the oven and the combined sample was immediately removed from the glass plate and allowed to cool lh. The samples were then carefully separated and inspected for adhesion or peeling of the coating.
The glass fiber gridding cloth is a first layer, a second layer and a third layer from top to bottom, and the test result is based on the adhesion or stripping condition of the coating on each layer of glass fiber gridding cloth. No blocking-the coating was tacky and did not show any signs of blocking on the surface of the coating when the samples were separated. Slight adhesion-when the samples were separated, some adhesion occurred on the surface of the coating, but the coating did not stretch upon separation and was not damaged after separation. Moderate adhesion, i.e., a certain degree of adhesion occurs on the surface of the coating, the coating stretches when separated, but the coating is not damaged after separation. Severe adhesion: the surface of the coating is sticky, and part of the coating is damaged in the separation process. And (3) complete adhesion: the coating is completely adhered or the coating on the glass fiber cloth is mixed and can not be separated.
The test results of examples 1A to 1I and comparative examples 1A to 1I are as follows.
From the above, the siloxane is added to the oil phase liquid, so that the siloxane is mixed into the shell structure, the adhesion and the bonding strength between the coating and the surface of the glass fiber can be improved, the anti-blocking property of the coating can be improved, and the possibility that the coating is peeled off from the glass fiber can be reduced.
In the second embodiment, the first embodiment of the method,
a preparation method of glass fiber mesh fabric latex is improved based on the first embodiment, siloxane is vinyl trimethoxy silane, corresponding latex is obtained, and an adhesion peeling test is carried out, wherein the test result is as follows.
In the third embodiment, the first step is that,
a preparation method of glass fiber mesh fabric latex is improved based on the first embodiment, 3-butylene triethoxysilane is used as siloxane, corresponding latex is obtained, and an adhesion peeling test is carried out, wherein the test result is as follows.
As can be seen from the second and third examples, when the siloxane is an alkenyl siloxane, the siloxane can be polymerized with a butadiene monomer and a styrene monomer, and the siloxane is grafted into a butadiene-styrene polymerization system, so that the compatibility of the siloxane in the butadiene-styrene polymerization system is enhanced; the siloxane which is connected into the butadiene-styrene polymerization system can be crosslinked, the crosslinking degree in the butadiene-styrene polymerization system is improved, the bonding strength of the coating is improved, the siloxane is grafted into the butadiene-styrene polymerization system and then is combined with the surface of the glass fiber, the adhesive force and the bonding strength between the coating and the surface of the glass fiber are further improved, and the possibility that the coating is peeled off from the glass fiber is further reduced.
Meanwhile, vinyl siloxane is grafted into a butadiene-styrene polymerization system and is influenced by steric hindrance, vinyl carried by the vinyl siloxane is prevented from continuing to perform polyaddition, and the chain length and the molecular weight of the butadiene-styrene polymerization system are limited, so that the adhesive strength of the coating is improved, the grafting amount of the vinyl siloxane connected into the butadiene-styrene polymerization system is increased, the adhesive force and the adhesive strength of the coating and glass fibers are enhanced through the siloxane, and the possibility that the coating is peeled off from the glass fibers is further reduced.
In the fourth embodiment, the first step is that,
a process for the preparation of a glass fibre scrim latex, modified from that of example 1A, except that the siloxane is 3- (2, 3-glycidoxy) propyltrimethoxysilane and the aqueous liquid comprises 25 to 35kg of an alkenyl carboxylic acid, the components of the aqueous liquid being as follows.
The production was carried out according to the process, giving examples 4A-4I corresponding to aqueous liquids B1-B9, example 4A corresponding to aqueous liquid B1, example 4B corresponding to aqueous liquid B2, and so on. And comparative examples 4A-4j were set up. Comparative examples 4A-4I: based on examples 4A-4I, the difference is that the siloxane is dimethylsiloxane. Comparative example 4 j: based on example 1A, the difference is that the siloxane is 3- (2, 3-glycidoxy) propyltrimethoxysilane.
The latexes obtained in examples 4A to 4I and comparative examples 4A to 4j were subjected to a blocking peeling test, and the test results are as follows.
(1) Examples 4A to 4I
(2) Comparative examples 4A to 4j
According to the method, alkenyl carboxylic acid is added into the aqueous phase liquid, epoxy alkyl siloxane is selected as silane, the alkenyl carboxylic acid is introduced into a butadiene-styrene polymerization system, the epoxy alkyl siloxane is grafted on the alkenyl carboxylic acid, and the epoxy alkyl siloxane grafted into the polymerization system is crosslinked with siloxane on other polymer chains, so that the crosslinking degree in the butadiene-styrene polymerization system is improved, and the coating bonding strength is improved; meanwhile, siloxane is grafted into a polymerization system and then is combined with the surface of the glass fiber, so that the adhesive force and the bonding strength between the coating and the surface of the glass fiber are further improved, and the possibility of peeling off the coating from the glass fiber is reduced.
In the fifth embodiment, the first step is,
a preparation method of glass fiber mesh cloth latex is improved based on the embodiment 1A, and is characterized in that a coupling agent is formed by compounding N-hydroxymethyl acrylamide and N-octyl methacrylamide, the mass ratio of the N-hydroxymethyl acrylamide to the N-octyl methacrylamide is 1:1-1.5, and the components of an aqueous phase liquid are as follows.
The production was carried out according to the process, giving examples 5A-5C corresponding to aqueous liquids B10-B12, example 5A corresponding to aqueous liquid B10, example 5B corresponding to aqueous liquid B11, and example 5C corresponding to aqueous liquid B12. And comparative example 5A, comparative example 5A: based on example 1A, the difference is that the crosslinker is N-methylolacrylamide.
The latexes obtained in examples 5A to 5C and comparative example 5A were subjected to a blocking peeling test, and the test results are as follows.
| Example 5A | Example 5B | Example 5C | Comparative example 5A | |
| First layer | No adhesion | No adhesion | No adhesion | Slight adhesion |
| Second layer | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion |
| Third layer | Slight adhesion | Slight adhesion | Slight adhesion | Moderate adhesion |
From the above, it is known that N-methylol acrylamide and N-alkyl octyl methacrylamide are used in combination as a cross-linking agent, so that the blocking resistance of the coating is improved, and the possibility that the coating is peeled off from the glass fiber is reduced.
In the sixth embodiment, the process is carried out,
the preparation method of the glass fiber mesh cloth latex is improved based on the first embodiment, the latex raw material further comprises 15-20kg of consistency regulating liquid, the consistency regulating liquid is prepared by mixing DOPO and ethanol, and the consistency regulating liquid comprises the following components.
| Consistency control fluid A | Consistency regulator B | Consistency control fluid C | |
| DOPO/kg | 8 | 10 | 9 |
| Ethanol/kg | 25 | 27 | 30 |
A preparation method of glass fiber mesh cloth latex comprises the following steps,
s1: vacuumizing a polymerization kettle, adding 15-35kg of styrene, 50-65kg of butadiene, 10-15kg of emulsifier and 300kg of water 250-;
s2: uniformly mixing 70-90kg of styrene and 1-3kg of chain transfer agent, adding 40-55kg of butadiene, uniformly mixing, adding 5-10kg of siloxane, and uniformly mixing to obtain oil phase liquid;
s3: 3-8kg of cross-linking agent, 250-320kg of water and other raw materials of water phase liquid are uniformly mixed to obtain water phase liquid;
s4: uniformly mixing 7-12kg of second initiator and 90-130kg of water to obtain initiator solution;
s5: adding 15-20kg of seed latex and 150kg of water 130-containing organic solvent into another polymerization kettle, stirring, uniformly mixing, heating to 75 ℃, adding 140kg of water phase liquid 120-containing organic solvent and 150kg of oil phase liquid 130-containing organic solvent, simultaneously dropwise adding 6-10kg of initiator solution, wherein the dropwise adding completion time is 1-2h, after the dropwise adding, carrying out heat preservation reaction for 1-2h, and controlling the temperature to be 80-90 ℃; adding dropwise consistency regulating solution 15-20kg for 1-2h, controlling the temperature at 80-90 deg.C after dropwise addition, reacting for 1-2h, and distilling to remove ethanol after reaction;
s6: after ethanol is removed, the liquid in the polymerization kettle is gradually cooled to below 30 ℃ to obtain the product latex.
The following examples 6A-6I were obtained according to the above procedure, with the following parameters.
Comparative example 6A and comparative example 6B were set simultaneously.
Comparative example 6A: a method of preparing a fiberglass scrim latex, based on example 1A, in S5: adding seed latex and water into another polymerization kettle, stirring, uniformly mixing, heating to 75 ℃, adding water-phase liquid and oil-phase liquid, simultaneously dropwise adding an initiator solution, wherein the dropwise adding time is 1-2h, and after the dropwise adding is finished, carrying out heat preservation reaction for 1-2h, and controlling the temperature to be 80-90 ℃; then adding 18kg of dropwise ethanol for 1-2h, controlling the temperature at 80-90 ℃ after the dropwise addition, keeping the temperature for reacting for 1-2h, and distilling to remove the ethanol after the reaction is finished.
Comparative example 6B: a method of preparing a fiberglass scrim latex, based on example 1A, in S5: adding seed latex and water into another polymerization kettle, stirring, uniformly mixing, heating to 75 ℃, adding water-phase liquid and oil-phase liquid, simultaneously dropwise adding an initiator solution, wherein the dropwise adding time is 1-2h, and after the dropwise adding is finished, carrying out heat preservation reaction for 1-2h, and controlling the temperature to be 80-90 ℃; then adding 9kg of DOPO, controlling the temperature at 80-90 ℃, and keeping the temperature to react for 1-2 hours.
The latexes obtained in examples 6A to 6I, comparative example 6A and comparative example 6B were subjected to the blocking peeling test, and the test results are as follows.
| Example 6A | Example 6B | Example 6C | Example 6D | Example 6E | Example 6F | |
| First layer | No adhesion | No adhesion | No adhesion | No adhesion | No adhesion | No adhesion |
| Second layer | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion |
| Third layer | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion |
| Example 6G | Example 6H | Example 6I | Comparative example 6A | Comparative example 6B | ||
| First layer | No adhesion | No adhesion | No adhesion | Slight adhesion | Slight adhesion | |
| Second layer | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion | Slight adhesion | |
| Third layer | Slight adhesion | Slight adhesion | Slight adhesion | Moderate adhesion | Moderate adhesion |
From the above, DOPO has P-H bond, which can react with carbon-carbon double bond, reduce saturation, block polymerization process, adjust polymerization system molecular weight, adjust latex viscosity and coating viscosity, improve coating anti-blocking property, and reduce possibility of coating peeling off from glass fiber. Meanwhile, DOPO needs to be dissolved in ethanol and dispersed in liquid in a polymerization kettle along with the dispersion of the ethanol, so that the dispersion is more uniform, and the DOPO grafting reaction is facilitated. On the other hand, the ethanol steam is carried along with the distillation removal of the ethanol to remove residual polymer monomers and micromolecule byproducts in the latex, thereby improving the anti-blocking property of the coating and reducing the possibility of the coating peeling off from the glass fiber.
The latex-cured coatings obtained in examples 6A-6I, comparative example 6A, and comparative example 6B were further subjected to a flame resistance test in accordance with the UL94 flame resistance standard, with the following results.
| Example 6A | Example 6B | Example 6C | Example 6D | Example 6E | Example 6F | |
| Flame resistance rating | V-1 | V-1 | V-1 | V-1 | V-1 | V-1 |
| Example 6G | Example 6H | Example 6I | Comparative example 6A | Comparative example 6B | ||
| First layer | V-1 | V-1 | V-1 | HB | HB |
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (4)
1. A glass fiber mesh fabric latex is characterized in that: the emulsion is prepared from the following raw materials in parts by mass through emulsion polymerization:
15-20 parts of seed latex,
130 portions and 150 portions of oil-phase liquid,
120-140 portions of water-phase liquid,
6-10 parts of an initiator solution,
100 portions and 120 portions of soft water,
15-20 parts of consistency adjusting liquid,
the seed latex is prepared by mixing the following raw materials in parts by mass: 15-35 parts of styrene, 50-65 parts of butadiene, 10-15 parts of emulsifier, 2-3.5 parts of first initiator and 300 parts of water 250-;
the oil phase liquid is prepared by mixing the following raw materials in parts by weight: 70-90 parts of styrene, 40-55 parts of butadiene, 1-3 parts of a chain transfer agent and 5-10 parts of siloxane;
the water-phase liquid comprises the following raw materials in parts by weight: 3-8 parts of a cross-linking agent and 150 parts of water 130-;
the initiator solution is prepared by mixing the following raw materials in parts by mass: 7-12 parts of a second initiator and 90-130 parts of water;
the consistency regulating liquid is prepared by mixing the following raw materials in parts by weight: 8-10 parts of DOPO and 25-30 parts of ethanol.
2. A fiberglass scrim latex according to claim 1, wherein: the siloxane is an alkenyl siloxane.
3. A fiberglass scrim latex according to claim 2, wherein: the alkenyl siloxane is vinyl siloxane.
4. A method of preparing a glass fibre scrim latex according to any of claims 1 to 3, wherein: comprises the following steps of (a) carrying out,
s1: vacuumizing a polymerization kettle, adding 15-35 parts of styrene, 50-65 parts of butadiene, 10-15 parts of emulsifier and 300 parts of water 250-containing material at one time, stirring, heating to 40-60 ℃, adding 2-3.5 parts of first initiator, keeping the temperature, continuously stirring for reaction for 10-25 hours, and cooling to below 30 ℃ after the reaction reaches more than 98% of conversion rate to obtain seed latex;
s2: uniformly mixing 70-90 parts of styrene and 1-3 parts of chain transfer agent, adding 40-55 parts of butadiene, uniformly mixing, adding 5-10 parts of siloxane, and uniformly mixing to obtain an oil phase liquid;
s3: uniformly mixing 3-8 parts of cross-linking agent and 320 parts of water 250-320 to obtain water phase liquid;
s4: uniformly mixing 7-12 parts of a second initiator and 90-130 parts of water to obtain an initiator solution;
s5: adding 15-20 parts of seed latex and 150 parts of water 130-containing organic solvent into another polymerization kettle, stirring, uniformly mixing, heating to 75 ℃, adding 140 parts of water-phase liquid and 150 parts of oil-phase liquid, simultaneously dropwise adding 6-10 parts of initiator solution, wherein the dropwise adding completion time is 1-2h, after the dropwise adding, carrying out heat preservation reaction for 1-2h, and controlling the temperature to be 80-90 ℃; adding 15-20 parts of dropwise consistency regulating liquid for 1-2h, controlling the temperature at 80-90 ℃ after dropwise addition, keeping the temperature for reaction for 1-2h, and distilling to remove ethanol after the reaction is finished;
s6: after ethanol is removed, the liquid in the polymerization kettle is gradually cooled to below 30 ℃ to obtain the product latex.
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|---|---|---|---|---|
| DD219782A1 (en) * | 1983-12-14 | 1985-03-13 | Buna Chem Werke Veb | METHOD FOR THE PRODUCTION OF CARBOXYLLATICES FOR FLEECE FASTENING |
| CN104311739A (en) * | 2014-11-14 | 2015-01-28 | 杭州蓝诚实业有限公司 | Organic silicone modified styrene-butadiene latex and a preparation method thereof |
| CN106749917A (en) * | 2016-11-30 | 2017-05-31 | 杭州蓝诚新材料有限公司 | Fabric coating styrene-butadiene latex and preparation method thereof |
| CN108659158A (en) * | 2018-05-31 | 2018-10-16 | 枣阳市恒泰化工有限公司 | A kind of modified glass-fiber grid cloth special-purpose latex and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6184287B1 (en) * | 1999-01-26 | 2001-02-06 | Omnova Solutions Inc. | Polymeric latexes prepared in the presence of 2-acrylamido-2-methylpropanesulfonate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD219782A1 (en) * | 1983-12-14 | 1985-03-13 | Buna Chem Werke Veb | METHOD FOR THE PRODUCTION OF CARBOXYLLATICES FOR FLEECE FASTENING |
| CN104311739A (en) * | 2014-11-14 | 2015-01-28 | 杭州蓝诚实业有限公司 | Organic silicone modified styrene-butadiene latex and a preparation method thereof |
| CN106749917A (en) * | 2016-11-30 | 2017-05-31 | 杭州蓝诚新材料有限公司 | Fabric coating styrene-butadiene latex and preparation method thereof |
| CN108659158A (en) * | 2018-05-31 | 2018-10-16 | 枣阳市恒泰化工有限公司 | A kind of modified glass-fiber grid cloth special-purpose latex and preparation method thereof |
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