CN109517545A - A kind of SBS adhesive and preparation method thereof - Google Patents
A kind of SBS adhesive and preparation method thereof Download PDFInfo
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- CN109517545A CN109517545A CN201811391764.2A CN201811391764A CN109517545A CN 109517545 A CN109517545 A CN 109517545A CN 201811391764 A CN201811391764 A CN 201811391764A CN 109517545 A CN109517545 A CN 109517545A
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
- C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
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- 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
- C09J11/06—Non-macromolecular additives organic
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention discloses a kind of SBS adhesive and preparation method thereof.The SBS adhesive according to the mass fraction, including following components: combination rubber: 9.9~10.5 parts；Mixed solvent: 57.1~63 parts；Oleum: 1.2~1.8 parts；Butadiene-styrene rubber: 2.5~4.5 parts；Tackifying resin: 21~21.9 parts；Anti-aging agent: 0.1~0.2 part.The preparation method of the SBS adhesive includes the following steps: that rubber will be combined under S1, room temperature is dissolved completely in the mixed solvent, obtains mixed liquor；S2, oleum is added in the mixed liquor that S1 is obtained, urea methanol solution is added after bringing it about sulfonating reaction 2h~4h；S3, styrene butadiene rubber sbr 1502, tackifying resin and anti-aging agent is added, stirring and dissolving uniformly filters to arrive SBS adhesive afterwards.The present invention can under low temperature, high humidity environment the metal wire frame of rapid link color lamp and color lamp cloth, the adhesive strength of the adhesive slow, the demand that can satisfy hot environment and put on display for a long time that reduces speed after bonding, and low toxic and environment-friendly.
Description
Technical field
The present invention relates to chemical material technical fields, and in particular to a kind of SBS adhesive and preparation method thereof.
Background technique
Zi Gong lamp can be with a long history, has formd the artistic characteristics that large-scale, material is polynary, intension is abundant at present." from
Tribute color lamp " becomes Chinese tradition color lamp cultural industry reputable brand, and color lamp industry long-term practitioner in Zi Gong is high up to more than 40,000 people
The peak phase, annual value of production was more than 2,000,000,000 yuan up to more than 80,000 people, and Zi Gong color lamp lamp can be in more than 50 a countries and regions and the country more than 500
A big and medium-sized cities are put on display, and add up to see lamp number up to more than 10 hundred million times.
Zi Gong color lamp manual fabrication procedures and the technique of expression include guide frame welding, butt-joint moulding, color separation paper, iuuminting,
Hand drawing pattern, paper-cut stickup etc..Zi Gong color lamp is required according to art, and moulding plating is welded on the metal support frame Jing Guo moulding
Zinc-iron silk (i.e. guide frame), then the various colored color lamp cloth such as gluing exterior trim lace, paper eight pieces of satin, Se Dingbu.All kinds of adhesive exist
Dosage is very big in the production of Zi Gong color lamp, papers for metal wire frame with color lamp cloth and Nian Jie SBS adhesive dosage surpasses every year
Cross 2000 tons.
But color lamp uses adhesive mainly to select solvent type SBS super glue as adhesive, these adhesive at present
It has the following problems: 1) poor, fail to stick with glued material cohesion when rainy weather, humidity are larger；2) in cold
Winter, solvent volatilization is slow, and adhesive tack is poor, and the viscosity of adhesive reduces；3) hold viscosity it is bad, stability is poor,
It is easy to fall off under big, the dry environment of wind；4) summer high temperature and 1 year or more long period put on display SBS elastomer because aging, bonding are strong
Degree declines and fails；5) there is VOC pollution problem to some extent, when construction generates biggish harm to human body.
Since there are the above problem, existing SBS adhesive is not able to satisfy the need of color lamp production and long period lantern show now
It asks, limits the development and popularization of the meeting of Zi Gong lamp.Therefore, how to solve the above technical problem, exploitation high-adhesive-strength, low temperature,
The adhesive of energy rapid link becomes the developing direction of Zi Gong color lamp special-purpose adhesive under high humidity environment.
Summary of the invention
In view of the above shortcomings of the prior art, existing in color lamp production it is an object of the invention to solve
Viscosity is low under low temperature, high humidity environment for adhesive, hold the poor, viscose glue of viscosity after adhesive strength reduce it is fast and the problems such as pollute environment,
A kind of SBS adhesive is provided, can under low temperature, high humidity environment the metal wire frame of rapid link color lamp and color lamp cloth, hold viscosity
Enhance, the adhesive strength reduction speed of the adhesive is slow after bonding, the demand that can satisfy hot environment and put on display for a long time, and low
Poison ring is protected.The present invention also provides a kind of preparation methods of SBS adhesive, and the preparation method is simple, are readily produced operation.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that it is such:
A kind of SBS adhesive, the adhesive according to the mass fraction, including following components:
Combination rubber: 9.9~10.5 parts；Mixed solvent: 57.1~63 parts；The oleum that concentration is 20%: 1.2~1.8 parts；
Butadiene-styrene rubber: 2.5~4.5 parts；Tackifying resin: 21~21.9 parts；Anti-aging agent: 0.1~0.2 part.
Further, the combination rubber is made of SBS792, SIS1105 and star-shaped sbs LG411, wherein SBS792,
SIS1105, star-shaped sbs LG411 mass parts ratio be 4.3~4.5:2.8~3.0:2.8~3.0.The present invention uses SBS792
SIS1105(styrene-isoprene-is added as basic rubber in (styrene-butadiene-styrene triblock copolymer)
Styrene triblock copolymer) and star-shaped sbs LG411, significantly improve the toughness and tack of SBS adhesive, SBS adhesive
Viscosity also significantly improve, convenient in color lamp manufacturing process the manual brushing SBS adhesive.
Further, the mixed solvent is by toluene, butyl acetate, ethyl acetate, acetone, 6# solvent naphtha and methylene chloride group
It is 8.5:0.5 at the mass parts ratio of, wherein toluene, butyl acetate, ethyl acetate, acetone, 6# solvent naphtha and methylene chloride:
4.8~5.0:3.5~4.0:35~40:4.8~5.0.Due to using the mixed solvent of mentioned component and proportion composition, SBS
The tack of adhesive improves, the open hour shorten, convenient for producer's manual operations under low temperature in winter；And above-mentioned mixing is molten
Agent can improve mixed solvent polarity, the urea methanol solution that when combination rubber after capable of dissolving sulfonation modifying and sulfonation is added,
To obtain the SBS adhesive of homogeneous transparent.
Further, the tackifying resin is made of terpene resin T-100, C5 Petropols and rosin, wherein terpene resin
The mass parts ratio of T-100, C5 Petropols and rosin is 9.5~10.0:7.2~7.4:4.3~4.5.
Further, the anti-aging agent is antioxidant 1010 or antioxidant 4020.
The present invention also provides a kind of preparation methods of SBS adhesive, include the following steps:
Combination rubber is dissolved completely in the mixed solvent under S1, room temperature, obtains mixed liquor；
S2, the oleum that concentration is 20% is added in the mixed liquor that S1 is obtained, stirring brings it about sulphur at 20 DEG C~40 DEG C
Change reaction 2h~4h, the urea methanol solution that concentration is 20% is added after reaction, restores, neutralize extra oleum；
S3, styrene butadiene rubber sbr 1502, tackifying resin and anti-aging agent, stirring and dissolving are added in the solution after the sulfonation that S2 is obtained
Filtering is after uniformly to get the SBS adhesive for arriving brown color homogeneous transparent.
Further, in the step S2, the mass fraction of urea methanol solution is 1.8~2.4.
Compared with prior art, the present invention has the advantage that
1, unique formula of the invention enables SBS adhesive in low temperature, high humidity environment since each components compatibility interacts
The metal wire frame and color lamp cloth of lower rapid link color lamp, and hold sticky enhancing, low toxic and environment-friendly；The adhesive adhesive strength is at 18
Actual measurement Average Bond Strength reduces by 27.9% in month, is dropped by less than 30%, can satisfy the metal wire frame and color lamp long period of color lamp
Bonding, thus meet color lamp long period exhibition requirement.
2,20% oleum sulfonation is used in sulfonation process due to the present invention, polarity improves after rubber sulfonation, increase pair
The adhesive force of glued material, while sulfonation introduces highly acid sulfonic acid group on rubber molecule, to metal and various color lamp cloth
Material cementability significantly improves；Sulfonation modifying SBS initial bond strenght under low temperature, high humidity environment is high, convenient in winter, rainy season
Rapid construction.Compared with using 98% concentrated acid sulfonation, the present invention does not generate incompatible with mixed solvent in sulfonation process
Water, adhesive homogeneous transparent obtained, storage stability are good；And compared with using chlorosulfuric acid, the present invention uses oleum
Sour cost is lower.Therefore, the Adhensive performance not only obtained using oleum sulfonation is more preferable, but also cost is lower, largely makes
It is with good economic efficiency with great amount of cost can be saved.
3, the pH value of the solution in conventionally employed NaOH and after extra sulfonating agent, adjusting sulfonation, the product after reaction is not
It can be dissolved in the mixed solvent, obtained mixed solution is muddy；And the present invention is using the reduction of 20% urea methanol solution, neutralization
Extra oleum, the product after reaction can be dissolved in the mixed solvent, and form homogeneous system, to obtain uniformly saturating
Bright adhesive.
4, using first SBS792, SIS1105 and star-shaped sbs LG41 are combined the combination rubber sulfonation to be formed processing, then plus
Enter tackifying resin, styrene butadiene rubber sbr and anti-aging agent, can be avoided tackifying resin, styrene butadiene rubber sbr and anti-aging agent oxidation in sulfonation
It is oxidized in the process and effect reduction, it is ensured that tackifying resin, styrene butadiene rubber sbr and anti-aging agent can give full play to its effect.
5, the preparation method of SBS adhesive provided by the invention is simple, is readily produced operation.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment one:
By SBS792, SIS1105 and star-shaped sbs LG411 by the combination that mass fraction is that 4.4:2.9:2.9 is mixed under S1, room temperature
Rubber is dissolved completely in the mixed solvent, obtains mixed liquor.The mixed solvent is by toluene, butyl acetate, ethyl acetate, third
Ketone, 6# solvent naphtha and methylene chloride composition, wherein toluene, butyl acetate, ethyl acetate, acetone, 6# solvent naphtha and methylene chloride
Mass parts ratio be 8.5:0.5:4.9:3.7:38:4.9.
S2, in the mixed liquor that S1 is obtained be added mass fraction be 1.6, the oleum that concentration is 20%, stirred at 35 DEG C
Mix and bring it about sulfonating reaction 3.5h, after sulfonating reaction be added mass fraction be 2.2 20% urea methanol solution reduction,
Extra oleum is neutralized, restores, neutralize extra oleum.
S3, styrene butadiene rubber sbr 1502, mass parts that mass fraction is 4.2 are added in the solution after the sulfonation that S2 is obtained
The antioxidant 1010 and tackifying resin that number is 0.15, stirring and dissolving uniformly filter to arrive the SBS glue of brown color homogeneous transparent afterwards
Stick.Wherein, the tackifying resin is made of terpene resin T-100, C5 Petropols and rosin, terpene resin T-100, C5 stone
The mass parts ratio of oleoresin and rosin blend is 9.7:7.3:4.3.
Embodiment two:
By SBS792, SIS1105 and star-shaped sbs LG411 by the combination that mass fraction is that 4.4:2.9:2.9 is mixed under S1, room temperature
Rubber is dissolved completely in the mixed solvent, obtains mixed liquor.The mixed solvent is by toluene, butyl acetate, ethyl acetate, third
Ketone, 6# solvent naphtha and methylene chloride composition, wherein toluene, butyl acetate, ethyl acetate, acetone, 6# solvent naphtha and methylene chloride
Mass parts ratio be 8.5:0.5:4.9:3.7:38:4.9.
S2, in the mixed liquor that S1 is obtained be added mass fraction be 1.2, the oleum that concentration is 20%, stirred at 35 DEG C
Mix and bring it about sulfonating reaction 3h, after sulfonating reaction be added mass fraction be 1.8 20% urea methanol solution reduction, in
With extra oleum, restores, neutralizes extra oleum.
S3, styrene butadiene rubber sbr 1502, mass parts that mass fraction is 3.5 are added in the solution after the sulfonation that S2 is obtained
The antioxidant 1010 and tackifying resin that number is 0.15, stirring and dissolving uniformly filter to arrive the SBS glue of brown color homogeneous transparent afterwards
Stick.Wherein, the tackifying resin is made of terpene resin T-100, C5 Petropols and rosin, terpene resin T-100, C5 stone
The mass parts ratio of oleoresin and rosin blend is 9.7:7.3:4.3.
Embodiment three:
Embodiment three is not sulfonated SBS adhesive, is comparative test.It is SBS792:SIS1105 by mass fraction: star-like
The combination rubber of SBS LG411:SBR1502=4.4:2.9:2.9, mass fraction are terpene resin T-100:C5 Petropols: pine
Perfume (or spice)=9.7:7.3:4.3 tackifying resin, the antioxidant 1010 of mass fraction 0.15 are dissolved in the mixed solvent, be configured to without
The SBS adhesive of sulfonation modifying.Wherein, mixed solvent is by toluene, butyl acetate, ethyl acetate, acetone, 6# solvent naphtha and dichloro
Methane composition, toluene, butyl acetate, ethyl acetate, acetone, 6# solvent naphtha and methylene chloride mass parts ratio be 8.5:0.5:
4.9:3.7:38:4.9.
The performance test results of SBS adhesive obtained in embodiment one to three are as shown in the table:
| Performance | Embodiment one | Embodiment two | Embodiment three |
| Appearance | It is brown color clear homogeneous thick liquid, no suspended substance, miscellaneous without visible machinery Matter and phenomenon of phase separation | It is brown color clear homogeneous thick liquid, no suspended substance, miscellaneous without visible machinery Matter and phenomenon of phase separation | The uniform thick liquid of yellow transparent, no suspended substance, without visible machinery Impurity and phenomenon of phase separation |
| Tensile shear strength/MPa | 1.48 | 1.41 | 1.18 |
| Open hour/min | 11 | 12 | 16 |
| Viscosity/(mPa.s) | 2730 | 2760 | 2900 |
| Initial adhesive strength/MPa | 1.04 | 0.92 | 0.76 |
| Dry heat resistance energy | 60 DEG C without bubbling, without phenomenon of coming unglued | 60 DEG C without bubbling, without phenomenon of coming unglued | 60 DEG C without bubbling, without phenomenon of coming unglued |
| Water resistance (25 DEG C, water logging Bubble is for 24 hours) | Nothing is come unglued | Nothing is come unglued | It comes unglued |
| Total volatile organism/ (g/L) | 61.7 | 62.2 | 62.4 |
| Non-volatile content/% | 38 | 37.3 | 37.3 |
| It is bonded after 18 months strong Degree/MPa | 0.75 | It comes unglued | It comes unglued |
Embodiment one, embodiment are second is that using the preparation method in the present invention, by the SBS adhesive of sulfonation modifying, embodiment
Third is that the not sulphur-modified obtained SBS adhesive of embodiment one.As can be known from the above table: the SBS adhesive of embodiment one is just viscous strong
Degree are as follows: 1.04MPa, open hour 11min, tensile shear strength 1.48Mpa improve 25% compared with embodiment three；Embodiment
Two SBS adhesive initial adhesive strength are as follows: 0.92MPa, open hour 12min, tensile shear strength 1.41Mpa are relatively implemented
Example three improves 19%.The SBS adhesive water resistance of embodiment one and embodiment two is preferable, impregnates in 25 DEG C of water and does not open for 24 hours
Glue, and without bubbling under 60 DEG C of environment, without phenomenon of coming unglued.The SBS adhesive comprehensive performance that embodiment one obtains is better than embodiment
Two obtained SBS adhesive.SBS adhesive made from embodiment one and implementation two complies with standard " styrene-butadiene-benzene
Ethylene block copolymer (SBS) adhesive " GB/T 27561-2011 requirement.
SBS adhesive in embodiment three comes unglued in or so half a year, and the SBS of embodiment two, which is adhesive in 1 year or so, to come unglued.It is real
Applying the SBS adhesive of example one adhesive strength after 18 months is 0.75Mpa, compared with initial adhesive strength decline 27.9%.Compared to embodiment
Two and embodiment three made from SBS adhesive, SBS adhesive adhesive property made from embodiment one is more preferable, when being bonded after use
Between more long, and the metal wire frame that can satisfy color lamp without coming unglued and the macrocyclic bonding of color lamp can be used for a long time, thus
Meet the requirement of color lamp long period exhibition.
In conclusion SBS adhesive adhesive strength provided by the invention is high, the open hour are short, viscosity is high, brush without stream
Drop down, be bonded adhesive strength in 18 months be reduced below 30%, water-tolerant, dry heat resistance can it is good, meet " styrene-butadiene-
Styrene block copolymer (SBS) adhesive " GB/T 27561-2011 requirement.
Finally, it should be noted that technical side the above examples are only used to illustrate the technical scheme of the present invention and are not limiting
Case, those skilled in the art should understand that, modification or equivalent replacement of the technical solution of the present invention are made for those, and
The objective and range for not departing from the technical program, are intended to be within the scope of the claims of the invention.
Claims (7)
1. a kind of SBS adhesive, it is characterised in that: the adhesive according to the mass fraction, including following components:
Combination rubber: 9.9~10.5 parts；Mixed solvent: 57.1~63 parts；The oleum that concentration is 20%: 1.2~1.8 parts；
Butadiene-styrene rubber: 2.5~4.5 parts；Tackifying resin: 21~21.9 parts；Anti-aging agent: 0.1~0.2 part.
2. SBS adhesive according to claim 1, it is characterised in that: the combination rubber by SBS792, SIS1105 and
Star-shaped sbs LG411 composition, wherein SBS792, SIS1105, star-shaped sbs LG411 mass parts ratio be 4.3~4.5:2.8~
3.0:2.8~3.0.
3. SBS adhesive according to claim 1, it is characterised in that: the mixed solvent is by toluene, butyl acetate, second
Acetoacetic ester, acetone, 6# solvent naphtha and methylene chloride composition, wherein toluene, butyl acetate, ethyl acetate, acetone, 6# solvent naphtha
Mass parts ratio with methylene chloride is 8.5:0.5:4.8~5.0:3.5~4.0:35~40:4.8~5.0.
4. SBS adhesive according to claim 1, it is characterised in that: the tackifying resin is by terpene resin T-100, C5
Petropols and rosin composition, wherein the mass parts ratio of terpene resin T-100, C5 Petropols and rosin be 9.5~
10.0:7.2~7.4:4.3~4.5.
5. SBS adhesive according to claim 1, it is characterised in that: the anti-aging agent is antioxidant 1010 or anti-aging agent
4020。
6. a kind of preparation method for preparing SBS adhesive as described in any one in claim 1-5, it is characterised in that: including such as
Lower step:
Combination rubber is dissolved completely in the mixed solvent under S1, room temperature, obtains mixed liquor；
S2, the oleum that concentration is 20% is added in the mixed liquor that S1 is obtained, stirring brings it about sulphur at 20 DEG C~40 DEG C
Change reaction 2h~4h, the urea methanol solution that concentration is 20% is added after reaction, restores, neutralize extra oleum；
S3, styrene butadiene rubber sbr 1502, tackifying resin and anti-aging agent, stirring and dissolving are added in the solution after the sulfonation that S2 is obtained
Filtering is after uniformly to get the SBS adhesive for arriving brown color homogeneous transparent.
7. the preparation method of SBS adhesive according to claim 6, it is characterised in that: in the step S2, urea methanol
The mass fraction of solution is 1.8~2.4.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004843A (en) * | 2021-03-02 | 2021-06-22 | 江苏凯伦建材股份有限公司 | Novel self-adhesive waterproof material |
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| Publication number | Publication date |
|---|---|
| CN109517545B (en) | 2021-01-05 |
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