CN108753091A - A kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent - Google Patents
A kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent Download PDFInfo
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- CN108753091A CN108753091A CN201810659991.2A CN201810659991A CN108753091A CN 108753091 A CN108753091 A CN 108753091A CN 201810659991 A CN201810659991 A CN 201810659991A CN 108753091 A CN108753091 A CN 108753091A
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- styrene rubber
- symmetric block
- rubber class
- conditioning agent
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Gloves (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention belongs to symmetric block butadiene-styrene rubber class sole inorganic agent technical fields, and in particular to a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent includes the raw material of following parts by weight：20-26 parts of (methyl) crylic acid hydroxy ester, 4-6 parts of polyadipate -1,4- butanediol esters, 1-3 parts of dodecafluoroheptyl methacrylate, 0.03-0.07 parts of three sodium nitride, 1-3 parts of onion essential oil, 0.2-0.4 parts of initiator, 100 parts of double solvents.The present invention has the following advantages compared with prior art：By by each raw material rational proportion in the present invention, it is capable of the inorganic agent of forming properties stabilization, the initial adhesive strength of inorganic agent, eventually viscous intensity and wellability can be ensured by meeting the use of solvent, properties of product are stablized, surface polarity, activity and the roughness of symmetric block butadiene-styrene rubber class sole can be improved after use, improve the peel strength between footwear material, nontoxic, not yellowing, suitable for promoting the use of.
Description
Technical field
The invention belongs to symmetric block butadiene-styrene rubber class sole inorganic agent technical fields, and in particular to a kind of symmetric block
Butadiene-styrene rubber class sole surface conditioning agent.
Background technology
Shoes can be regarded as being glued " bridging " agent between material and adhesive with surface conditioning agent, and effect is to remove quilt
Contamination, greasy dirt and the processing aid etc. of viscous material surface, while one layer of new superficial layer can be formed being glued material surface, change
Surface polarity, activity, roughness of material etc. are glued, is allowed to match with used adhesive, improves peel strength,
Found in actual use, peel strength and holding power are not only related with the performance of adhesive, also with glued material surface polarity,
Activity is related with roughness, and in existing shoemaking industry, the thermoplastic elastomer processed based on symmetric block butadiene-styrene rubber is wide
General use, but since its polarity is weaker, difficulty is bonded, and inorganic agent sym-closene stability is poor, easy yellowing can pollute shoes
Face, therefore, it is necessary to study a kind of free of contamination surface conditioning agent.
Invention content
The purpose of the present invention is for existing problem, provide at a kind of symmetric block butadiene-styrene rubber class sole surface
Manage agent.
The present invention is achieved by the following technical solutions：A kind of symmetric block butadiene-styrene rubber class sole surface treatment
Agent includes the raw material of following parts by weight：20-26 parts of (methyl) crylic acid hydroxy ester, 4-6 parts of polyadipate -1,4- butanediol esters,
1-3 parts of dodecafluoroheptyl methacrylate, 0.03-0.07 parts of three sodium nitride, 1-3 parts of onion essential oil, 0.2-0.4 parts of initiator,
100 parts of double solvents；
The preparation method of the onion essential oil is：By fresh onion clean after and mass concentration 6-8% chitosan aqueous solution with
Weight ratio 1:1 mixing is crushed after homogenate avoid light place 2-3 hours under conditions of temperature is 1-5 DEG C, obtains homogenate, complete
Homogenate is filtered afterwards, separating filtrate and residue, then by filtrate and petroleum ether with weight ratio 1:2-4 is mixed, and is 34- in temperature
Extracted 4 hours in 38 DEG C of water-bath, detach water-yielding stratum and oil reservoir, oil reservoir is distilled under conditions of 52-58 DEG C to get.
As further improvement of these options, (methyl) crylic acid hydroxy ester is hydroxy-ethyl acrylate, metering system
One kind in sour hydroxyl ethyl ester, hydroxypropyl acrylate, hydroxy propyl methacrylate or acrylic acid -4- hydroxybutyls.
As further improvement of these options, double solvents includes 18-22 parts of raw material butanone, the 3- of following parts by weight
4-8 parts of pentanone, 1-5 parts of N,N-dimethylformamide, 40-60 parts of deionized water.
As further improvement of these options, the initiator is in azodiisobutyronitrile, azobisisoheptonitrile
It is a kind of.
As further improvement of these options, the deacetylation of the chitosan is 74-78%.
As further improvement of these options, aqueous solution is the acetic acid water that mass concentration is 1% in chitosan aqueous solution
Solution.
As further improvement of these options, preparation method is, in temperature after above-mentioned raw materials are mixed according to the ratio
It under conditions of 85-90 DEG C, is stirred to react 4-6 hours, discharges after cooling to obtain the final product.
As further improvement of these options, the process that is stirred to react carries out under nitrogen atmosphere；The stirring
Mixing speed is 65-75 revs/min when reaction.
The present invention has the following advantages compared with prior art：By that by each raw material rational proportion, can be formed in the present invention
The inorganic agent that performance is stablized, the initial adhesive strength of inorganic agent, eventually viscous intensity and wellability, production can be ensured by meeting the use of solvent
Moral character can be stablized, and can improve surface polarity, activity and the roughness of symmetric block butadiene-styrene rubber class sole after use, improve footwear material
Between peel strength, nontoxic, not yellowing, suitable for promoting the use of.
Specific implementation mode
Embodiment 1
A kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent, includes the raw material of following parts by weight：(methyl) acrylic acid
23 parts of hydroxy ester, 5 parts of polyadipate -1,4- butanediol esters, 2 parts of dodecafluoroheptyl methacrylate, 0.05 part of three sodium nitride, ocean
2 parts of green onion essential oil, 0.3 part of initiator, 100 parts of double solvents；
The preparation method of the onion essential oil is：After fresh onion is cleaned and 7% chitosan aqueous solution of mass concentration is with weight
Measure ratio 1:1 mixing is crushed after homogenate avoid light place 2.5 hours under conditions of temperature is 3 DEG C, obtains homogenate, after the completion will
Homogenate filters, separating filtrate and residue, then by filtrate and petroleum ether with weight ratio 1:3 mixing, the water for being 36 DEG C in temperature
Extracted 4 hours in bath, detach water-yielding stratum and oil reservoir, oil reservoir is distilled under conditions of 55 DEG C to get.
Wherein, (methyl) crylic acid hydroxy ester is hydroxy-ethyl acrylate.
Wherein, double solvents includes 6 parts of 20 parts of raw material butanone, the propione of following parts by weight, n,N-Dimethylformamide
3 parts, 50 parts of deionized water.
Wherein, the initiator is azodiisobutyronitrile.
Wherein, the deacetylation of the chitosan is 74-78%；It is 1% that aqueous solution, which is mass concentration, in chitosan aqueous solution
Aqueous acetic acid.
Wherein, preparation method is after mixing above-mentioned raw materials according to the ratio under conditions of temperature is 88 DEG C, to be stirred to react
It 5 hours, discharges after cooling to obtain the final product.
Wherein, the process that is stirred to react carries out under nitrogen atmosphere；Mixing speed when being stirred to react is 70 revs/min
Clock.
Embodiment 2
A kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent, includes the raw material of following parts by weight：(methyl) acrylic acid
20 parts of hydroxy ester, 6 parts of polyadipate -1,4- butanediol esters, 1 part of dodecafluoroheptyl methacrylate, 0.07 part of three sodium nitride, ocean
3 parts of green onion essential oil, 0.2 part of initiator, 100 parts of double solvents；
The preparation method of the onion essential oil is：After fresh onion is cleaned and 8% chitosan aqueous solution of mass concentration is with weight
Measure ratio 1:1 mixing is crushed after homogenate avoid light place 3 hours under conditions of temperature is 1 DEG C, obtains homogenate, after the completion will be even
Slurries filter, separating filtrate and residue, then by filtrate and petroleum ether with weight ratio 1:2 mixing, the water-bath for being 38 DEG C in temperature
Middle extraction 4 hours, detaches water-yielding stratum and oil reservoir, oil reservoir is distilled under conditions of 52 DEG C to get.
Wherein, (methyl) crylic acid hydroxy ester is hydroxyethyl methacrylate.
Wherein, double solvents includes 8 parts of 18 parts of raw material butanone, the propione of following parts by weight, n,N-Dimethylformamide
1 part, 60 parts of deionized water.
Wherein, the initiator is azobisisoheptonitrile.
Wherein, the deacetylation of the chitosan is 74-78%；It is 1% that aqueous solution, which is mass concentration, in chitosan aqueous solution
Aqueous acetic acid.
Wherein, preparation method is after mixing above-mentioned raw materials according to the ratio under the conditions of at a temperature of 90 °C, to be stirred to react
It 4 hours, discharges after cooling to obtain the final product.
Wherein, the process that is stirred to react carries out under nitrogen atmosphere；Mixing speed when being stirred to react is 65 revs/min
Clock.
Embodiment 3
A kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent, includes the raw material of following parts by weight：(methyl) acrylic acid
26 parts of hydroxy ester, 4 parts of polyadipate -1,4- butanediol esters, 3 parts of dodecafluoroheptyl methacrylate, 0.03 part of three sodium nitride, ocean
1 part of green onion essential oil, 0.4 part of initiator, 100 parts of double solvents；
The preparation method of the onion essential oil is：After fresh onion is cleaned and 6% chitosan aqueous solution of mass concentration is with weight
Measure ratio 1:1 mixing is crushed after homogenate avoid light place 2 hours under conditions of temperature is 5 DEG C, obtains homogenate, after the completion will be even
Slurries filter, separating filtrate and residue, then by filtrate and petroleum ether with weight ratio 1:4 mixing, the water-bath for being 34 DEG C in temperature
Middle extraction 4 hours, detaches water-yielding stratum and oil reservoir, oil reservoir is distilled under conditions of 58 DEG C to get.
Wherein, (methyl) crylic acid hydroxy ester is acrylic acid -4- hydroxybutyls.
Wherein, double solvents includes 4 parts of 22 parts of raw material butanone, the propione of following parts by weight, n,N-Dimethylformamide
5 parts, 40 parts of deionized water.
Wherein, the initiator is azobisisoheptonitrile.
Wherein, the deacetylation of the chitosan is 74-78%；It is 1% that aqueous solution, which is mass concentration, in chitosan aqueous solution
Aqueous acetic acid.
Wherein, preparation method is after mixing above-mentioned raw materials according to the ratio under conditions of temperature is 85 DEG C, to be stirred to react
It 6 hours, discharges after cooling to obtain the final product.
Wherein, the process that is stirred to react carries out under nitrogen atmosphere；Mixing speed when being stirred to react is 75 revs/min
Clock.
Control group 1 is set, polyadipate in embodiment 1-1,4-butanediol ester is removed, remaining content is constant；Setting
Control group 2 removes dodecafluoroheptyl methacrylate in embodiment 1, remaining content is constant；Control group 3 is set, by embodiment
Onion essential oil removes in 1, remaining content is constant；Control group 4 is set, three sodium nitrides in embodiment 1 are removed, remaining content is not
Become；Control group 5 is set, chitosan aqueous solution in embodiment 1 is substituted for etc. to the water of weight, remaining content is constant；Setting control
Group 6, is substituted for aliquots of deionized water, remaining content is constant by double solvents in embodiment 1；
Choice experiment material is TPR soles and corium, and adhesive is monocomponent polyurethane JM-1015P glue, straight after corium polishing
Uniform gluing both sides are connect, TPR soles are handled with above-mentioned each group surface conditioning agent, and processing method is to dip surface treatment with cotton
Agent wipes TPR sole surfaces, is dried at 75 DEG C, then uniform gluing 2 times, is dried at 65 DEG C, initial adhesive strength is surveyed after room temperature curing,
Viscous intensity eventually is surveyed by GB/T2791-1995 after 24 hours, puller system is LJ-5000 type puller systems, not have at surface conditioning agent
Reason is blank group；
Obtain following result：
Table 1
Initial adhesive strength compared with prior art is can be seen that in the present invention by data in table 1 and viscous intensity is greatly improved eventually,
Properties of product are stablized, it is observed that after coating without yellowing after 30 days.
Claims (9)
1. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent, which is characterized in that include the raw material of following parts by weight：
20-26 parts of (methyl) crylic acid hydroxy ester, 4-6 parts of polyadipate -1,4- butanediol esters, dodecafluoroheptyl methacrylate 1-3
Part, 0.03-0.07 parts of three sodium nitride, 1-3 parts of onion essential oil, 0.2-0.4 parts of initiator, 100 parts of double solvents；
The preparation method of the onion essential oil is：By fresh onion clean after and mass concentration 6-8% chitosan aqueous solution with
Weight ratio 1:1 mixing is crushed after homogenate avoid light place 2-3 hours under conditions of temperature is 1-5 DEG C, obtains homogenate, complete
Homogenate is filtered afterwards, separating filtrate and residue, then by filtrate and petroleum ether with weight ratio 1:2-4 is mixed, and is 34- in temperature
Extracted 4 hours in 38 DEG C of water-bath, detach water-yielding stratum and oil reservoir, oil reservoir is distilled under conditions of 52-58 DEG C to get.
2. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as described in claim 1, which is characterized in that (methyl)
Crylic acid hydroxy ester is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate or third
One kind in olefin(e) acid -4- hydroxybutyls.
3. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as described in claim 1, which is characterized in that compound molten
Agent includes 1-5 parts of 4-8 parts of 18-22 parts of raw material butanone, propione, the N,N-dimethylformamide of following parts by weight, deionized water
40-60 parts.
4. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as described in claim 1, which is characterized in that described to draw
Hair agent is one kind in azodiisobutyronitrile, azobisisoheptonitrile.
5. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as described in claim 1, which is characterized in that the shell
The deacetylation of glycan is 74-78%.
6. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as described in claim 1, which is characterized in that chitosan
Aqueous solution is the aqueous acetic acid that mass concentration is 1% in aqueous solution.
7. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as described in claim 1, which is characterized in that it is prepared
Method is after mixing above-mentioned raw materials according to the ratio under conditions of temperature is 85-90 DEG C, to be stirred to react 4-6 hours, go out after cooling
Expect to obtain the final product.
8. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as claimed in claim 7, which is characterized in that described to stir
Reaction process is mixed to carry out under nitrogen atmosphere.
9. a kind of symmetric block butadiene-styrene rubber class sole surface conditioning agent as claimed in claim 7, which is characterized in that described to stir
Mixing speed is 65-75 revs/min when mixing reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810659991.2A CN108753091B (en) | 2018-06-25 | 2018-06-25 | Surface treating agent for symmetric block styrene-butadiene rubber type soles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810659991.2A CN108753091B (en) | 2018-06-25 | 2018-06-25 | Surface treating agent for symmetric block styrene-butadiene rubber type soles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108753091A true CN108753091A (en) | 2018-11-06 |
| CN108753091B CN108753091B (en) | 2020-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810659991.2A Active CN108753091B (en) | 2018-06-25 | 2018-06-25 | Surface treating agent for symmetric block styrene-butadiene rubber type soles |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072902A (en) * | 1999-09-07 | 2001-03-21 | Minolta Co Ltd | Ink jet recording solution |
| CN1296044A (en) * | 1999-11-12 | 2001-05-23 | 陈光宇 | Low surface energy repelling type dirt-proof paint and use method thereof |
| CN101113308A (en) * | 2007-07-24 | 2008-01-30 | 中国建筑材料科学研究总院 | Interface additive for improving interface bond strength of polyurethane pellicle and organic glass |
| CN101942767A (en) * | 2010-07-28 | 2011-01-12 | 丽水市优耐克水性树脂科技有限公司 | Interior wall adornment leather and preparation method |
| CN105968460A (en) * | 2016-05-23 | 2016-09-28 | 华南协同创新研究院 | Method for preparing rubber by using onion essential oil as rubber regenerant |
| CN107903868A (en) * | 2017-12-15 | 2018-04-13 | 阜阳市龙建包装材料有限公司 | A kind of water-proof antibiotic adhesive for polyurethane |
-
2018
- 2018-06-25 CN CN201810659991.2A patent/CN108753091B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072902A (en) * | 1999-09-07 | 2001-03-21 | Minolta Co Ltd | Ink jet recording solution |
| CN1296044A (en) * | 1999-11-12 | 2001-05-23 | 陈光宇 | Low surface energy repelling type dirt-proof paint and use method thereof |
| CN101113308A (en) * | 2007-07-24 | 2008-01-30 | 中国建筑材料科学研究总院 | Interface additive for improving interface bond strength of polyurethane pellicle and organic glass |
| CN101942767A (en) * | 2010-07-28 | 2011-01-12 | 丽水市优耐克水性树脂科技有限公司 | Interior wall adornment leather and preparation method |
| CN105968460A (en) * | 2016-05-23 | 2016-09-28 | 华南协同创新研究院 | Method for preparing rubber by using onion essential oil as rubber regenerant |
| CN107903868A (en) * | 2017-12-15 | 2018-04-13 | 阜阳市龙建包装材料有限公司 | A kind of water-proof antibiotic adhesive for polyurethane |
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| CN108753091B (en) | 2020-08-11 |
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