CN112442197B

CN112442197B - Aqueous SBS latex and method for preparing the same

Info

Publication number: CN112442197B
Application number: CN201910839267.2A
Authority: CN
Inventors: 唐建振; 吴光飞; 丁小卫
Original assignee: SHENZHEN ANPIN SILICONE MATERIAL CO Ltd
Current assignee: SHENZHEN ANPIN SILICONE MATERIAL CO Ltd
Priority date: 2019-09-05
Filing date: 2019-09-05
Publication date: 2023-01-17
Anticipated expiration: 2039-09-05
Also published as: CN112442197A

Abstract

The invention discloses a water-based SBS latex and a preparation method thereof, which improve the emulsifying property of SBS by a blending process, so that the prepared water-based SBS latex is stable and is not easy to break emulsion, the particle size of latex particles is small, the tensile strength and the elongation after film forming are high, the preparation process is simple, the cost is low, the safety and the environmental protection are realized, the use is convenient, the application range is wide, and the application prospect is good.

Description

Water-based SBS latex and preparation method thereof

Technical Field

The invention relates to the field of high polymer materials, and in particular relates to a water-based SBS latex and a preparation method thereof.

Background

SBS is short for styrene-butadiene-styrene block copolymer, has excellent tensile strength, large surface friction coefficient, good low-temperature performance, excellent electrical property, good processing performance and other characteristics, has incomparable advantages of thermosetting rubber in processing application, is a thermoplastic elastomer with the largest consumption at present, and is applied to the fields of asphalt modification, waterproof coating, adhesive and the like. For example, the asphalt is used for improving the high and low temperature resistance and the softening point of the asphalt in road construction; the SBS is added to the waterproof coiled material for modification, so that the elasticity, the elongation percentage, the corrosion resistance, the fatigue resistance, the service life of the waterproof coiled material and the like of the asphalt can be improved.

The application of SBS mostly relates to the mixing modification of SBS and other high molecular materials, in order to improve the modification efficiency, the method for preparing SBS into water-based latex is a mode with good application prospect, the prepared water-based latex is environment-friendly, convenient to transport, simple in application process, convenient to use, good in compatibility and SBS dispersibility, high energy consumption required by heating operation is avoided, and meanwhile, the application performance is convenient to adjust, and the application expansion is facilitated. However, SBS has a certain crystal structure, and has poor self-emulsifying property and is difficult to disperse, so that the aqueous latex dispersion system prepared according to the prior art mostly has the problems of low solid content, instability and easy demulsification. Meanwhile, in the prior art, SBS can be dissolved in organic solvents such as toluene and the like, and then the organic solvents are dispersed and emulsified, but the toluene belongs to a toxic solvent and is strictly limited in industrial application, so that development of a stable environment-friendly waterborne SBS emulsion product is greatly difficult, and the problem to be solved in the SBS application field is also urgent.

Disclosure of Invention

In order to solve the defects of the prior art, the invention aims to provide the water-based SBS latex and the preparation method thereof.

The invention provides a water-based SBS latex, which is prepared by mixing raw materials including SBS and blending agent to obtain a blending material, and then emulsifying and dispersing the blending material, wherein the blending agent comprises one or more unsaturated hydrocarbon compounds, and the mass percentage of groups only having unsaturated bonds in the unsaturated hydrocarbon compounds is 12-65%.

In some embodiments, the raw materials for preparing the blend material include tackifying resin to optimize the application properties of the SBS, and the kind and amount of tackifying resin are not particularly limited.

In some embodiments, the blending material is obtained by mixing SBS, blending agent and solvent, wherein the solvent is one or more of benzene, toluene, xylene, solvent gasoline, C6-C12 alkane, dichloroethane, methyl ethyl ketone, ethyl acetate and butyl acetate; wherein the C6-C12 alkane is a linear alkane, a branched alkane, a cycloalkane, or a cycloalkyl-containing alkane, such as cyclohexane, methylcyclohexane, n-octane, n-dodecane, or the like, and the boiling point of the solvent is less than the boiling point of the unsaturated hydrocarbon in the blending agent and less than the boiling point of water. More preferably, the mass ratio of the solvent to the blending agent is 1 to 2:1.

The mass percentage content of the groups only having unsaturated bonds in the unsaturated hydrocarbon compound is calculated as follows: x = M1/M0X 100%, where X is the mass percentage content of groups having only unsaturated bonds in the unsaturated hydrocarbon, M1 is the sum of the molar masses of groups having only unsaturated bonds in the unsaturated hydrocarbon, and M0 is the molar mass of the unsaturated hydrocarbon, as exemplified by the following compound myrcene:

the molar mass of the group having an unsaturated bond M1= M (= C = CH-) + M (= C = CH 2) + M (-CH = CH 2) =78, the molar mass of the unsaturated hydrocarbon M0=136, x = M1/M0 = 100% =57%.

In some embodiments, the unsaturated hydrocarbon is selected from one or more of a linear alkene, a branched alkene, a carbocyclic group-containing alkane, and a carbocyclic group-containing alkene, wherein the carbocyclic group does not include an aryl group and the carbocyclic group is a saturated or unsaturated 3-to 8-membered monocyclic, fused, or bridged ring. In some preferred embodiments, the unsaturated hydrocarbon compound contains at least 25% by mass of carbocyclic groups, and more preferably 35% to 70% by mass of carbocyclic groups, the method of calculating the mass% of carbocyclic groups being based on the mass% of groups having only unsaturated bonds in the unsaturated hydrocarbon compound.

In some preferred embodiments, the unsaturated hydrocarbon in the blending agent is selected from one or more of branched olefins, cyclic group-containing alkanes, cyclic group-containing alkenes. More preferably, the total mass percentage of branched olefins, alkanes containing cyclic groups, and alkenes containing cyclic groups in the blending agent is 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

Further, the branched olefin, the hydrocarbon group-containing alkane or the hydrocarbon group-containing alkene have a molecular formula conforming to the general formula (C5H 8) n, wherein n is 2, 3 or 4; preferably, n =2 or 3, more preferably the branched alkene, carbocyclic group containing alkane or carbocyclic group containing alkene is a monoterpene or sesquiterpene compound.

In some embodiments, the unsaturated hydrocarbon is selected from one or more of decene, camphene, zingiberene, camphene, limonene, neosyringatricyclene, santalene, phellandrene, myrcene, ocimene, terpinene, terpinolene, fenchylene, carene, zingiberene, sabinene, metaisoprene, limonene, myrcene, and pinene.

In some embodiments, the blending agent is a blend of one or more of lemon oil, mandarin oil, citrus oil, neroli oil, peppermint oil, camphor white oil, fir oil, pine oil, turpentine oil, eucalyptus oil, industrial dipentene, natural dipentene.

In some embodiments, the unsaturated hydrocarbon has a molecular weight of 95 to 280; preferably, it has a molecular weight of 110 to 240.

In some embodiments the unsaturated hydrocarbons have a boiling range in the range of 90 to 200 c, preferably in some embodiments the one or more unsaturated hydrocarbons present in the blending agent in the largest proportion have a boiling range in the range of 140 to 180 c, or in the range of 100 to 150 c. The boiling range of the unsaturated hydrocarbons in the blending agent directly affects the safety of the aqueous SBS latex and the removal efficiency after emulsification application, so as to reduce the influence of the blending agent on the application performance of the SBS material and the modified material.

In some embodiments, the weight ratio of the blending agent to SBS is (1.

The kind of the emulsifier is not particularly limited and is selected according to the actual situation, and it is preferable that in some embodiments, the emulsifier includes an anionic emulsifier and a nonionic emulsifier. In some embodiments, the anionic emulsifier is selected from the group consisting of a combination of one or more of carboxylate type, sulfonate type, sulfate type emulsifiers, and the nonionic emulsifier is selected from the group consisting of a combination of one or more of span 40, span 60, span 80, tween 60, tween 80, peregal, NP-10, AEO-3, AEO-5. In some preferred embodiments, the compounding ratio of the anionic emulsifier to the nonionic emulsifier is 2:1-5:1. Preferably, the emulsifier used for emulsification accounts for 0.5 to 3.5 percent of the total mass of the aqueous SBS latex.

Special additives including colloid protective agents, stabilizers, thickeners, sterilization and mildew inhibitors, antifoaming agents and the like can be added in the process of preparing the waterborne SBS latex through emulsification and dispersion so as to assist in improving the dispersion effect and the stability of the latex, and the types and the dosage of the special additives have no special requirements.

In another aspect of the present invention, there is provided a method for preparing the aqueous SBS latex, comprising the steps of:

mixing raw materials including SBS and blending agent to obtain blending material, adding emulsifier, stirring and dispersing, adding water and stirring to obtain water-based SBS latex.

The special auxiliary agents comprise colloid protective agents, stabilizing agents, thickening agents, sterilization and mildew proofing agents, defoaming agents and the like, and are added in the step of stirring and dispersing to form water-in-oil emulsion in the preparation method, or are added in the step of continuously adding emulsifying agents and water and stirring and emulsifying, and preferably are added after being mixed with water.

Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that at least one of the following is included:

the invention improves the emulsifying property of SBS by blending process, which makes the prepared water-based SBS latex stable and not easy to break emulsion, small in latex particle diameter, high in tensile strength and elongation after film forming, simple in preparation process, low in cost, safe and environment-friendly, convenient to use, wide in application range and good in application prospect.

Detailed Description

Specific examples of the aqueous SBS latex of the present invention and the method of preparing the same are given below.

An aqueous SBS latex is prepared by mixing raw materials including SBS and blending agent to obtain a blending material, and then emulsifying and dispersing the blending material to obtain the aqueous SBS latex, wherein the blending agent contains one or more unsaturated hydrocarbon compounds, and the mass percentage of groups only having unsaturated bonds in the unsaturated hydrocarbon compounds is 12-65%.

The SBS in the invention is a styrene-butadiene-styrene block copolymer, comprises linear and star structures, is optimized and selected through the block ratio (PS/PB) of the copolymer, the molecular structure category, the molecular weight and the like in practical application, and is not particularly limited.

The blending agent adopted by the invention has better 'softening' property to SBS, in particular to reduce the crystallinity of SBS and further reduce the difficulty of emulsification and dispersion, in some embodiments, SBS with molecular weight of 3-20W or even higher can be well emulsified, but the content of the blending agent can not be too small, otherwise the 'softening' is insufficient, or the viscosity of the formed blending material is too high, so that emulsification is difficult or emulsion breaking is easy, wherein, the lower the molecular weight of SBS, the less the required blending agent is, in some embodiments, SBS with molecular weight of 3-5W is adopted, stable SBS latex can still be obtained when the weight ratio of the blending agent to SBS is as low as 1; under the emulsification condition of high-speed shearing, the content of the blending agent can be further reduced; however, the content of the blending agent is not suitable to be too much, and the more the blending agent is, the lower the removal efficiency of the formed latex product in application, and the lower the resource and cost saving; thus, in some embodiments, a suitable weight ratio of the blending agent to SBS is 1. In some embodiments, the blended material has a viscosity of 200 to 5000mpa · s, and the aqueous SBS latex can be obtained by emulsifying and dispersing the blended material.

The unsaturated hydrocarbon in the blending agent is a nontoxic and environment-friendly compound and comprises a compound obtained by plant extraction and a derivative thereof; the blending agent is a compound which is in a liquid state at normal temperature so as to realize uniform mixing with SBS, or the blending agent is mixed with SBS and then heated to 20-35 ℃ so as to realize uniform mixing.

Generally, unsaturated hydrocarbon in the blending agent has too low molecular weight, low boiling point, is volatile, but is flammable and explosive, has higher danger and difficulty in production, storage and transportation, has high boiling point and higher safety when having too high molecular weight, but is often removed for a long time in application, and affects application performance and efficiency. Thus, in some embodiments, the molecular weight of the unsaturated hydrocarbon in the blending agent is between 95 and 280, or its boiling range is in the range of 90 to 200 ℃; preferably, it has a molecular weight in the range of 110 to 240 and a boiling range in the range of 140 to 180 ℃ or alternatively in the range of 100 to 150 ℃.

Meanwhile, the mass percentage content of the groups only having unsaturated bonds in the unsaturated hydrocarbon compound is calculated as follows: x = M1/M0X 100%, where X is the mass percentage content of groups having only unsaturated bonds in the unsaturated hydrocarbon, M1 is the sum of the molar masses of groups having only unsaturated bonds in the unsaturated hydrocarbon, and M0 is the molar mass of the unsaturated hydrocarbon, as exemplified by the following myrcene:

In some embodiments, the unsaturated hydrocarbon is selected from one or more of a linear alkene, a branched alkene, an alkane containing a carbocyclic group, an alkene containing a carbocyclic group, wherein the carbocyclic group does not include an aryl group, and the carbocyclic group is a saturated or unsaturated 3-to 8-membered monocyclic, fused, or bridged ring.

Preferably, the unsaturated hydrocarbon further satisfies at least one of the following:

it is a branched chain alkene;

which is an alkane containing a carbocyclic group,

which is an olefin containing carbocyclic groups.

In some preferred embodiments, the unsaturated hydrocarbon compound contains a carbocyclyl group in an amount of 25% by mass or more, and more preferably 35% to 70% by mass, the method for calculating the carbocyclyl group by mass being based on the method for calculating the unsaturated hydrocarbon compound by mass containing only groups having an unsaturated bond.

More preferably, the unsaturated hydrocarbon in the blending agent is at least one of a branched olefin, the cyclic group-containing alkane, and a cyclic group-containing olefin, and the mass of the branched olefin, the cyclic group-containing alkane, and the cyclic group-containing olefin is 70% or more, preferably 80% or more, and particularly preferably 90% or more of the total mass of the blending agent.

In some embodiments, the branched olefin, carbocyclic group-containing alkane, or carbocyclic group-containing alkene each have a formula according to general formula (C5H 8) n, wherein n is 2, 3, or 4; preferably, n =2 or 3, more preferably the branched alkene, carbocyclyl-containing alkane or carbocyclyl-containing alkene is a monoterpene or sesquiterpene compound.

In some embodiments, the unsaturated hydrocarbon is selected from the group consisting of a complex of one or more of decene, camphene, zingiberene, camphene, limonene, neosyringatricyclene, santalene, phellandrene, myrcene, ocimene, terpinene, terpinolene, fenchyene, carene, zingiberene, sabinene, metaisoprene, limonene, myrcene, and pinene.

Further, the blending agent may also contain minor amounts of terpene derivatives including oxygen-containing derivatives of terpene compounds, such as: alcohols, aldehydes, esters, acids, and derivatives thereof of varying degrees of saturation, wherein the monoterpene and sesquiterpene compounds have moderate molecular weights, the terpene derivatives are preferably monoterpene compounds or sesquiterpene compounds, or predominantly monoterpene or sesquiterpene compounds, and the impurities include non-terpene byproducts or natural products of terpenoid agent production and separation, and the like. The terpene compound is widely present in natural plants or animals, is biodegradable, and the blending agent can be an artificially synthesized or semi-synthesized substance or a natural extracted substance.

When the emulsifier adopted by the invention is an anionic emulsifier or the anionic emulsifier is compounded with a nonionic emulsifier, the emulsifying effect is good, and illustratively, the anionic emulsifier can be compounded with one or more of carboxylate type, sulfonate type and sulfate type emulsifiers; the non-ionic emulsifier can be selected from span 40, span 60, span 80, tween 60, tween 80, peregal, NP-10, AEO-3, and AEO-5. Preferably the anionic/nonionic built ratio is 1:1-8:1, more preferably 3:1-5:1.

When the water content in the system is too low, water-in-oil SBS latex can be formed after emulsification, and when the water content reaches a certain amount, oil-in-water latex can be formed, the method is selected according to the actual process, preferably, the water content in the oil-in-water SBS latex is 20-75% of the total weight of the SBS latex, and more preferably, 30-65%; the water-in-oil SBS latex comprises 7-18% of water by mass based on the total mass of the SBS latex.

The raw materials of the blending material preferably comprise tackifying resin, the tackifying resin and SBS are uniformly mixed, and then the mixture is further mixed with blending agent to obtain the blending material, the type and the dosage of the tackifying resin are not specially limited, and the blending material comprises one or more than two of hydrogenated petroleum resin, terpene resin, phenolic resin, C5/C9 resin, coumarone resin and modified rosin resin.

Special auxiliary agents including a cross-linking agent, a colloid protective agent, a stabilizing agent, a thickening agent, a sterilization mildew-proof agent, a defoaming agent and the like can be added in the process of preparing the water-based SBS latex through emulsification and dispersion so as to assist in improving the dispersion effect and the stability of the latex, and the type and the dosage of the special auxiliary agents have no special requirements. The cross-linking agent can be PVA or associated polyurethane thickening agent, and the colloid protective agent can be one or more than two of water-soluble polyurethane, water-soluble acrylic resin and water-soluble alkyd resin. The addition of the protective colloid can prevent the adhesion of particles in the latex by utilizing the electrostatic action on one hand, and can reduce the fluidity of the latex through viscosity adjustment on the other hand, thereby further improving the stability of the SBS latex; the addition of the sterilization and mildew-proof agent can avoid the phenomena of latex mildew, yellowing, color deepening and the like caused by the growth of various bacteria, fungi, algae and other microorganisms in water in the system, and can effectively prevent the latex from yellowing and smelling; in order to eliminate bubbles generated during the high shear process, a defoaming agent may be further added.

The preparation method of the waterborne SBS latex comprises the following steps:

mixing raw materials including SBS and blending agent to obtain blending material, adding emulsifier, stirring and dispersing, adding water, stirring and emulsifying to obtain the water-based SBS latex.

Wherein, the proportion and the definition of each component involved in the preparation method of the water-based SBS latex are as described in the foregoing.

In some embodiments, the feedstock for the preparation of the blended material further comprises a solvent, illustratively benzene, toluene, xylene, solvent gasoline, C6-C12 alkanes, dichloroethane, methyl ethyl ketone, ethyl acetate, butyl acetate; wherein the C6-C12 alkane is an alkane or cycloalkane, such as cyclohexane, n-hexane, n-octane, n-dodecane, and the like, preferably having a boiling point or boiling range less than that of the unsaturated hydrocarbon or solvent containing the unsaturated hydrocarbon, and more preferably less than that of water.

The viscosity of the blended material is critical to the formation and performance impact of the SBS latex, and it is desirable to control the viscosity within a certain range, in some embodiments, the blended material has a viscosity of 200 to 5000mpa.s at 25 ℃; particularly preferably 200 to 1000mpa.s.

In a specific embodiment, the mass ratio of the solvent to the blending agent is preferably (1-10): 1, which directly affects the viscosity of the blending material and the application performance of the final latex, on one hand, the addition of the solvent is favorable for reducing the viscosity of the blending material and promoting the softening of SBS, on the other hand, the addition of a part of the solvent can reduce the use of the blending agent and ensure that the blending material can be dispersed and emulsified to obtain stable latex, and the part of the solvent can be extracted from the system by vacuum distillation for several times by utilizing the difference of boiling points or boiling ranges after being dispersed and emulsified by adding water, so that the recycling is realized, part of water may be extracted in the process of vacuum distillation, but the amount of water in the system can be kept to realize the emulsification, and is adjusted according to the actual situation.

When the water content in the system is too low, water-in-oil SBS latex is formed firstly after emulsification, and when the water content reaches a certain amount, oil-in-water latex is formed, and the water-in-oil SBS latex is selected according to the actual process, preferably, the water content in the oil-in-water SBS latex is 20-75% of the total mass of the SBS latex, and more preferably, the water content in the oil-in-water SBS latex is 30-65% of the total mass of the SBS latex; the SBS latex is water-in-oil, the mass of the water accounts for 7 to 18 percent of the total mass of the SBS latex.

In order to improve the stability of the latex and reduce the particle size of the latex particles, which is beneficial for application, in some embodiments, the emulsifier is added, stirred and dispersed at a low speed of 400-1500r/min for 0.5-2h, and then the water is added, stirred and emulsified at a speed of 15000-25000r/min for 0.5-3h. In the process of adding the emulsifier, stirring, dispersing and adding water, stirring and emulsifying, the temperature of a reaction system can be increased to 50-80 ℃ to reduce the viscosity and facilitate emulsification, meanwhile, the temperature needs to be set to be lower than the boiling point of the solvent, the solvent can be removed through reduced pressure distillation, and the loss of water in the distillation process is reduced.

Example 1

200g of SBS colloidal particles (molecular weight is 11W, model is YH-792), 200g of limonene (molecular weight is 136.2, boiling point is 177 ℃, mass percent of double bond-containing group is 37.5%, mass percent of carbocyclyl is 58.8%) are put into a reaction kettle with a reflux device, the mixture is stirred and mixed uniformly at low speed of 500r/min at 50 ℃ to obtain a blended material (the viscosity at 25 ℃ is 660mpa.s by sampling test, the test method is to adopt NDJ-4 rotational viscometer measurement, a No. 2 rotor), 5g of sodium oleate, 10g of sodium didodecyl phenyl ether disulfonate and 5g of span 80 are slowly dripped, the stirring speed is adjusted to 1000r/min, after stirring and dispersing for 30min, the stirring speed is increased to 20000r/min, 50 ℃ water 280g is slowly dripped, after dripping is completed, the high-speed stirring at 50 ℃ for 1.5h is continued after 1h, and the waterborne SBS latex is obtained.

Example 2

200g of SBS (styrene butadiene styrene) colloidal particles (the molecular weight is 11W, and the model is YH-792), 160g of limonene (the molecular weight is 136.2, the boiling point is 177 ℃, the mass percentage of the group containing double bonds is 37.5%, and the mass percentage of the carbocyclyl group is 58.8%) are put into a closed reaction kettle with a reflux device, the temperature is raised to 50 ℃, the mixture is uniformly stirred and mixed at a low speed of 500r/min to obtain a blended material (the viscosity at 25 ℃ is 850mpa.s in a sampling test method, the testing method is that an NDJ-4 rotational viscometer is adopted for measurement, a No. 2 rotor), 5g of sodium oleate, 10g of sodium didodecyl phenyl ether disulfonate and 5g of span 80 are slowly dripped into the blended material, the stirring speed is adjusted to 1000r/min, after stirring and dispersing is carried out for 30min, the stirring speed is raised to 20000r/min, 220g of water is slowly dripped into the blended material, after dripping is completed in 1h, the blended material, the high speed is continuously stirred at a high speed of 20000r/min at 50 ℃ for 1.5h, the stirring speed is adjusted to 800r/min, 10g of water-soluble polyurethane, 0.2g of 0.2 min is added, the waterborne defoamer is continuously stirred, and the waterborne defoamer is filtered, and the waterborne bactericide is continuously filtered to obtain the waterborne bactericide after filtering is obtained.

Example 3

130g of SBS dry glue (molecular weight is 13W, product model is YH-791), 200g of natural dipentane (distillation range is 170-190 ℃,95%; xiamen Huayuan chemical industry Co., ltd.), 25g of terpene resin (Hubei Xinrunder chemical industry Co., ltd.), heating to 50 ℃ and stirring at low speed of 500r/min under constant temperature to obtain a blending material (sample testing shows that viscosity at 25 ℃ is 340mpa. S. The testing method is to adopt NDJ-4 rotational viscometer measurement, 2# rotor), slowly adding 5g of sodium abietate, 3g of sodium didodecyl phenyl ether disulfonate and 3g of AEO-3 dropwise, adjusting stirring speed to 1000r/min, stirring and dispersing for 30min, increasing stirring speed to 20000r/min, slowly adding 240g of hot water at 50 ℃ dropwise, stirring at high speed of 20000r/min for 1.5h after finishing dropwise adding at constant temperature within 1h, adjusting stirring speed to 800r/min, adding 15g of water-soluble acrylic resin, 0.3g of hot water, stirring for 0.30 min, filtering to obtain an aqueous defoaming agent, and continuously discharging.

Example 4

200g of SBS dry glue (molecular weight is 13W, product model is YH-791), 500g of toluene and 50g of natural dipentane (distillation range is 170-190 ℃,95%; xiamen heavy Huayuan chemical Co., ltd.) and stirring at a low speed of 500r/min to obtain a blended material (the 25 ℃ viscosity is 230mpa. S by sampling and testing, the testing method is to adopt NDJ-4 rotational viscometer to measure, a 2# rotor), heating to 65 ℃ and maintaining constant temperature, adjusting the vacuum degree to-0.5 kPa, distilling under reduced pressure for 1.5h, weighing and collecting 350g of toluene, stopping vacuumizing, slowly dropwise adding 5g of disproportionated rosin soap potassium and 1g NP-10 (Korea chemical engineering Co., ltd.), adjusting the stirring speed to 1000r/min, stirring and dispersing for 30min, then increasing the stirring speed to 20000r/min, slowly dropwise adding 90g of hot water with the temperature of 50 ℃, continuing to stir at a high speed for 1.5h after dropwise adding within 1h, adjusting the stirring speed to 800r/min, cooling to 50 ℃, continuing to start a vacuum pump to remove the remaining 150g of toluene, then adding 3g of water-soluble polyvinyl alcohol, 0.5g of PVA, 0.5g of mildew-proof bactericide, continuing to stir for 30min, and filtering the aqueous SBS to obtain the aqueous latex.

Example 5

200g of SBS dry glue (the molecular weight is 30W, the product model is YH-801), 150g of benzene, 50g of myrcene (the boiling point is 166-168 ℃, the mass percentage of the double-bond-containing group is 57 percent) and 50g of terpinene (Shanghai Tong Hao-Tech Biotech Co., ltd., the boiling point is 177.2 ℃, the mass percentage of the double-bond-containing group is 36.7 percent) are mixed in a closed reaction kettle with a reflux device, stirred at a low speed of 500r/min to obtain a blending material (the 25 ℃ viscosity is 470mpa.s by sampling test, the test method is that NDJ-4 rotational viscometer is adopted for measurement, a No. 2 rotor is adopted), the temperature is increased to about 65 ℃, and the vacuum degree is adjusted to-0.5 kPa, distilling under reduced pressure for about 1h, weighing and collecting 110g of distilled benzene, stopping vacuumizing, slowly dropwise adding 5g of disproportionated rosin soap potassium, 5g of sodium abietate and 3g of NP-10, adjusting the stirring speed to 1000r/min, stirring and dispersing for 30min, increasing the stirring speed to 18000r/min, slowly dropwise adding 270g of hot water with the temperature of 50 ℃, continuously stirring at the constant temperature of 50 ℃ for 1h and the high speed of 18000r/min for 1.5h at the constant temperature of 50 ℃, adjusting the stirring speed to 800r/min, cooling to 50 ℃, continuously starting a vacuum pump to pump out the remaining 40g of benzene, adding 1g of defoaming agent and 1g of mildew-proof bactericide, continuously stirring for 30min, discharging and filtering to obtain the aqueous SBS latex.

Example 6

In a closed reaction kettle with a reflux device, 200g of SBS dry glue (the molecular weight is 30W, the product model is YH-801), 200g of toluene and 80g of dipentene (the boiling point is 176-177 ℃, the product model is YH-801), stirring at a low speed of 500r/min to obtain a blending material (the viscosity at 25 ℃ is 440mpa. S by sampling and testing, the testing method is to adopt an NDJ-4 rotary viscometer and a 2# rotor), heating to 75 ℃ and keeping the constant temperature, adjusting the vacuum degree to-0.5 kPa, carrying out reduced pressure distillation for about 1.5h, weighing and collecting 150g of distilled toluene, stopping vacuumizing, slowly dropwise adding 15g of disproportionated rosin soap potassium and 5g of NP-10, adjusting the stirring speed to 1000r/min, stirring and dispersing for 30min, increasing the stirring speed to 22000r/min, slowly dropwise adding 220g of hot water with the temperature of 75 ℃, continuing to stir at high speed for 1.5h after the dropwise addition is completed within 1h, adjusting the stirring speed to 800r/min, cooling to 65 ℃, starting a vacuum pump to pump out 50g of the residual toluene, taking 80g of water and a small amount of emulsifier out, increasing the stirring speed to 22000r/min, stirring at normal pressure and high speed for 0.5h, then adjusting the stirring speed to 800r/min, adding 1g of defoaming agent and 1g of mildew-proof bactericide, continuing to stir for 30min, discharging and filtering to obtain the aqueous SBS latex.

Comparative example 1

200g of SBS dry glue (molecular weight is 30W, product model YH-801) and 280g of methylbenzene are mixed in a closed reaction kettle with a reflux device, stirring is carried out at low speed of 500r/min to obtain a blended material (viscosity is 470mpa.s in a sampling test, the test method is that NDJ-4 rotational viscometer is adopted for measurement, a 2# rotor is adopted), the temperature is increased to about 75 ℃, the vacuum degree is adjusted to-0.5 kPa, reduced pressure distillation is carried out for about 1.5h, 150g of distilled methylbenzene is weighed and collected, vacuumizing is stopped, 15g of disproportionated rosin soap potassium and 5g NP-10 are slowly dripped, the stirring speed is adjusted to 1000r/min, stirring and dispersion is carried out for 30min, the stirring speed is increased to 20000r/min, 75 ℃ hot water is slowly dripped to 220g, demulsification is completed in 1h, then high-speed stirring is continuously carried out for 1.5h, the stirring speed is adjusted to 800r/min, cooling is carried out to 65 ℃, a vacuum pump is started to remove residual methylbenzene, when about 220g of the collected, a small amount of white fine colloidal particles are separated out, a large amount of the methylbenzene is completely separated out, and a test is failed.

Comparative example 2

In a closed reaction kettle with a reflux device, 200g of SBS dry glue (molecular weight is 30W, product model YH-801), 200g of toluene and 80g of No. 200 solvent oil (Nakayasu chemical Co., ltd. In Maotai province), stirring at low speed of 500r/min to obtain a blended material (the viscosity at 25 ℃ is 510mpa.s in a sampling test by using NDJ-4 rotational viscometer, 2# rotor), heating to about 75 ℃, adjusting the vacuum degree to-0.5 kPa, distilling under reduced pressure for about 1.5h, weighing and collecting 150g of collected toluene, stopping vacuumizing, slowly dripping 15g of disproportionated rosin potassium soap and 5g of NP-10, adjusting the stirring speed to 1000r/min, stirring and dispersing for 30min, increasing the stirring speed to 20000r/min, slowly dripping 220g of 75 ℃ hot water, continuing to stir for 1.5h after dripping is completed for 1h, adjusting the stirring speed to 800r/min, cooling to 65 ℃, starting a vacuum pump to adjust the residual toluene, adding a small amount of distilled water and stirring water, adding a small amount of distilled water to 20000 min, continuously stirring for 1.5h after dripping is completed, stirring, continuously stirring to 800r/min, filtering the white water with a white water emulsifier and filtering to obtain a white defoamer, and filtering the white defoamer and filtering to obtain a defoamer.

Test example

The aqueous SBS latex prepared in each example and comparative example 2 was tested for properties as follows:

and (3) testing the emulsion performance:

1. and (4) testing the storage stability: 200g of aqueous SBS latex is put into a closed conical flask, put into an oven at 50 +/-2 ℃ and taken out after 30 days to observe the appearance of the latex.

2. Freeze-thaw stability: 50ml of the latex was put into a cylindrical plastic container or a glass container of about 100ml, and the container was sealed without mixing air bubbles, and then put into a low-temperature chamber of-5. + -. 2 ℃ for 18 hours, and then taken out, and further left to stand at 23. + -. 2 ℃ for 6 hours, and after repeating this for 3 times, the container was opened, and then stirred with a glass rod, and then the latex was applied onto a glass plate to obtain a uniform thin layer, and then the presence or absence of foreign matter such as flocs was observed.

3. Latex particle size testing: 2g of latex is diluted in 200g of deionized water and stirred uniformly, and the particle size is measured by a Winner2000ZD laser particle size analyzer.

4. Latex solid content test: tested with reference to GB-T2793-1995.

And (3) testing mechanical properties:

tensile strength, elongation test: the test is carried out according to the national standard GB/T1701-2001 method.

The preparation method of the tensile strength and elongation test sample comprises the following steps: and (3) coating the waterborne SBS latex on a clean glass plate by using a wet film preparation device, baking for 8 hours at the temperature of 60 ℃ to obtain a transparent paint film, taking down the paint film and cutting to obtain a test sample.

The test results are shown in Table 1.

TABLE 1

As can be seen from the data in Table 1, the latex of the invention has good stability, is an aqueous system, meets the requirement of environmental protection and has wide prospect in a plurality of SBS latex application fields.

The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims

1. An aqueous SBS latex is prepared by mixing raw materials including SBS and a blending agent to obtain a blending material, emulsifying and dispersing the blending material to obtain the aqueous SBS latex, wherein the blending agent comprises one or more unsaturated hydrocarbon, the unsaturated hydrocarbon only contains unsaturated bond groups with the mass percentage of 12-65%, the unsaturated hydrocarbon is one or more selected from straight chain unsaturated olefin, branched chain olefin, alkane containing carbon ring groups or alkene containing carbon ring groups, and the carbon ring groups are saturated or unsaturated 3-8-membered monocyclic, fused or bridged rings.

2. The aqueous SBS latex according to claim 1, wherein the unsaturated hydrocarbon contained in the blending agent is one or more of branched olefins, cyclic group-containing alkanes and cyclic group-containing alkenes.

3. The aqueous SBS latex according to claim 1 or 2 wherein the mass percentage of carbon ring groups in the unsaturated hydrocarbon is greater than or equal to 25%.

4. The aqueous SBS latex according to claim 2, wherein the unsaturated hydrocarbon in the blending agent is one or more of branched olefins, cyclic group-containing alkanes and cyclic group-containing alkenes, and the mass sum of the branched olefins, the cyclic group-containing alkanes and the cyclic group-containing alkenes accounts for 70% or more of the mass of the blending agent.

5. The aqueous SBS latex according to claim 4, wherein the branched olefins, cyclic carbon group containing alkanes and cyclic carbon group containing alkenes have a formula according to the general formula (C5H 8) n, wherein n is 2, 3 or 4.

6. The aqueous SBS latex according to claim 1, 4 or 5 wherein the unsaturated hydrocarbon has a molecular weight of 95 to 280 or the boiling range of the unsaturated hydrocarbon lies in the range of 90 to 200 ℃.

7. The aqueous SBS latex of claim 1, 4 or 5, wherein the unsaturated hydrocarbon is one or more of decene, camphene, limonene, neosyringatricyclene, santalene, phellandrene, myrcene, ocimene, terpinolene, fenchene, carene, zingiberene, sabinene, m-isoprene, limonene, myrcene, pinene.

8. The aqueous SBS latex of claim 1, 4 or 5, the blending agent is selected from one or more of lemon oil, mandarin oil, citrus oil, sweet orange oil, neroli oil, peppermint oil, camphor white oil, fir oil, pine oil, turpentine oil, eucalyptus oil, industrial dipentene, natural dipentene.

9. The aqueous SBS latex according to claim 1, wherein the weight ratio of the blending agent to SBS is (1.

10. The process for the preparation of aqueous SBS latex according to any one of claims 1 to 9, comprising the steps of:

11. The method for preparing aqueous SBS latex according to claim 10, wherein the raw materials for preparing the blended material further comprises tackifying resin.

12. The method for preparing aqueous SBS latex according to claim 10, wherein the raw materials for preparing the blended material further comprise a solvent, wherein the solvent is one or more of benzene, toluene, xylene, solvent gasoline, C6-C12 alkane, dichloroethane, methyl ethyl ketone, ethyl acetate and butyl acetate; wherein the C6-C12 alkane is straight-chain alkane, branched-chain alkane, cycloalkane or alkane containing cycloalkyl.

13. The method of preparing aqueous SBS latex of claim 12 wherein the boiling point, or the highest value of the boiling range, of the solvent is less than the boiling point, or the lowest value of the boiling range, of the unsaturated hydrocarbon and less than the boiling point of water.

14. The method for preparing aqueous SBS latex according to claim 12 or 13, wherein the mass ratio of the solvent to the blending agent in the blending material is 1.

15. The method for the preparation of aqueous SBS latex according to claim 12 or 13, wherein the method for the preparation of aqueous SBS latex further comprises a step of vacuum distillation to remove the solvent.