CN111073012A - TPR material surface treating agent and preparation method thereof - Google Patents
TPR material surface treating agent and preparation method thereof Download PDFInfo
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- CN111073012A CN111073012A CN201911415912.4A CN201911415912A CN111073012A CN 111073012 A CN111073012 A CN 111073012A CN 201911415912 A CN201911415912 A CN 201911415912A CN 111073012 A CN111073012 A CN 111073012A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a TPR material surface treating agent and a preparation method thereof, wherein the treating agent comprises 100-1000 parts of alkane solvent, 20-200 parts of ketone solvent, 20-150 parts of to-be-modified polymer matrix, 30-110 parts of composite vinyl grafting monomer, 1-5 parts of initiator, 2-6 parts of terminator and 15-45 parts of adhesion promoter. The principle of no trace of the matching of the double solvents and the TPE/SBS in the invention is that the solubility of the used solvents is relatively weak, the solvents do not belong to strong solvents, and the solvents have general dissolving capacity for solid substances, so molecular chains of the solid substances are not completely stretched, the solid content and viscosity of the treating agent are controlled to be lower, only 3-5%, and the viscosity is 10-100, so the coating amount of the treating agent is smaller, meanwhile, the solvents have low corrosivity for the base material, and the treating agent basically does not leave obvious traces on the base material after being dried by combining various factors.
Description
Technical Field
The invention relates to a TPR material surface treating agent, in particular to a TPR material surface treating agent without leaving traces after drying and a preparation method thereof.
Background
At present, most of surface treating agents of TPR shoe materials in the shoe making industry are solvents with high hazard such as toluene, xylene and the like as main solvent components, solid components mainly comprise various chloroprene rubbers, SBS high polymer materials and various additives, and the treating agents have high viscosity and solid content and good treatment effect due to good solubility of benzene. However, the method has the problems that the toxicity of the product is relatively high, the product is not environment-friendly, and an important problem is that after the TPR treating agent is coated and dried, obvious treating traces can be seen on the surface of the material, workers can inevitably coat the material beyond the boundary range during coating, traces left on parts which do not need to be attached are obvious, the cleaning is difficult, and the appearance influence is brought to the finished product shoes. It would be a clear great advance to the shoe making process if the TPR treatment agent could be brushed and dried without leaving traces or with traces that are not obvious.
Disclosure of Invention
In view of the above, the invention provides a surface treating agent for a TPR material and a preparation method thereof, which not only solve the problems that the surface treating agent for the TPR material is easy to leave bright traces on a base material after being coated, so that obvious traces are easy to leave at positions where the surface treating agent overflows after being coated, and the surface treating agent is difficult to clean, but also improve the problem that the traditional TPR treating agent has high toxicity, the traditional TPR treating agent takes triphenyl as a main solvent, has high toxicity, and has high dissolving power, so that the surface of the material is seriously damaged, and simultaneously, the solid content and the viscosity of the treating agent are relatively high, so that obvious traces can be left. According to the invention, the more environment-friendly alkane solvent is mainly used for grafting modification of TPE and SBS macromolecules, and then the adhesion promoter is added in a proper amount at the later stage, so that on the premise of ensuring the treatment effect, no mark is left after painting, and meanwhile, the toxicity is greatly reduced.
In order to solve the technical problems, the invention adopts the following technical scheme:
the TPR material surface treating agent comprises the following components in parts by weight:
100-1000 parts of alkane solvent, 10-100 parts of butanone solvent, 20-150 parts of polymer matrix to be modified, 30-110 parts of composite vinyl grafting monomer, 1-5 parts of initiator, 2-6 parts of terminator, 15-45 parts of adhesion promoter and 10-100 parts of acetone diluent.
Further, the polymer matrix to be modified comprises 10-100 parts of rubber matrix and 10-50 parts of resin matrix.
Further, the rubber matrix is modified macromolecule TPE1475, and the resin matrix is SBS 1401.
Further, the vinyl grafting monomer comprises 20-80 parts of methacrylic acid grafting monomer (MMA), 5-15 parts of hydroxyethyl methacrylate grafting monomer (2HEMA) and 5-15 parts of acrylic acid grafting monomer (AA).
Further, the alkane solvent is methylcyclohexane.
Further, the initiator is dibenzoyl peroxide (BPO), and the terminator is dibutyl hydroxy toluene (BHT).
Further, the adhesion promoter comprises 5-10 parts of vinyl chloride-vinyl acetate resin P710 (Shanghai Pan high chemical industry), 5-20 parts of chlorinated rubber S20 (Germany Bayer), and 5-15 parts of multifunctional resin AMS-110 (Tanshigao high-new modified materials Co., Ltd., Wuxi city).
The preparation method of the TPR material surface treating agent comprises the following steps:
s1, mixing an alkane solvent and a butanone solvent, putting the mixture into a water bath, starting stirring, adding a polymer matrix to be modified, and heating to 80-90 ℃ until the solid is completely dissolved;
s2, adding vinyl grafting monomers, adding an initiator, starting to react, keeping the temperature constant at 80-90 ℃, reacting for 4-5 hours, paying attention to the change of the viscosity and the appearance in the whole process, and adding a terminator to terminate after the required viscosity is reached;
s3, cooling to 45-50 ℃, adding the adhesion promoter and the acetone diluent, fully stirring and dissolving for 2 hours, and finishing the whole process to obtain the TPR material surface treating agent.
According to the invention, the more environment-friendly alkane solvent and the ketones are taken as main materials, the TPE/SBS to-be-modified polymer matrix is subjected to graft modification, and then the adhesion promoter is added in a proper amount at the later stage, so that on the premise of ensuring the treatment effect, bright marks can not be left after the coating treatment agent is dried, and the toxicity is greatly reduced.
Meanwhile, the polymer matrix to be modified is mainly a modified thermoplastic elastomer TPE/SBS, the solid and TPR have the same polarity by grafting modification through a vinyl composite monomer, and meanwhile, a proper amount of adhesion promoter is added to improve the adhesion to the material.
According to the invention, a mixed monomer (2HEMA/MMA/AA) is adopted for grafting modification in a grafting method, so that the structure has irregularity and polarity, and has better affinity to a TPR material.
The adhesion promoters (P710, AMS-110 and S20) are added at the later stage to further improve the treatment effect.
The matching of the solvent and the solid ensures that the treating agent has good treatment effect, and does not leave bright traces which are difficult to remove after the brushing treating agent is dried. The principle of no trace is that the solubility of the used solvent is relatively weak, the solvent does not belong to a strong solvent, the dissolving capacity of the solvent for the solid matter is general, so that the molecular chain of the solid matter is not completely stretched, the solid content and the viscosity of the treating agent are controlled to be lower, only 3-5 percent and the viscosity is 10-100, so that the coating amount of the treating agent is smaller, the corrosivity of the solvent for the base material is not strong, and the treating agent basically does not leave obvious traces on the base material after being dried by combining various factors.
Detailed Description
In order that those skilled in the art will more clearly and intuitively understand the present invention, the present invention will be further described below.
Example 1
The TPR material surface treating agent comprises the following components in parts by weight:
100g of alkane solvent-methylcyclohexane, 10g of ketone solvent-acetone, 10g of ketone solvent-butanone, 10g of TPE1475, 10g of SBS1401, 20g of MMA grafting monomer, 5g of 2HEMA grafting monomer, 5gAA grafting monomer, 1g of BPO initiator, 2g of BHT terminator, 5g of P710 adhesion promoter, 5g of chlorinated rubber S20 adhesion promoter and 5g of AMS-110 adhesion promoter.
The preparation method of the TPR material surface treating agent of the embodiment includes the following steps:
1. adding butanone and methylcyclohexane into a flask with stirring, putting the flask into a water bath, adding modified high polymer solid substances TPE1475 and SBS1401, and heating to 80-90 ℃ until the solids are completely dissolved;
2. adding vinyl grafting monomer: MMA, 2HEMA and AA, then adding initiator BPO, starting the reaction, keeping the temperature constant at 80-90 ℃, reacting for 4-5 hours, paying attention to the change of the viscosity and appearance in the whole process, adding BHT to terminate after the required viscosity is reached, controlling the reaction viscosity at 150-300cps/25 ℃, gradually changing the appearance from transparent to turbid, and adding terminator to terminate after the required viscosity is reached;
3. cooling to 40-50 ℃, adding an adhesion promoter: p710, AMS-110, S20, adding acetone for dilution, fully stirring and dissolving for 2 hours, and finishing the whole process.
Example 2
The TPR material surface treating agent comprises the following components in parts by weight:
600g of alkane solvent-methylcyclohexane, 80g of ketone solvent-acetone, 80g of ketone solvent-butanone, 60g of high-molecular TPE1475, 30g of high-molecular SBS1401, 50g of MMA grafting monomer, 10g of 2HEMA grafting monomer, 10gAA grafting monomer, 3g of BPO initiator, 4g of BHT terminator, 8g of P710 adhesion promoter, 15g of chlorinated rubber S20 adhesion promoter and 10g of AMS-110 adhesion promoter.
The preparation method is the same as that of example 1.
Example 3
The TPR material surface treating agent comprises the following components in parts by weight:
1000g of alkane solvent-methylcyclohexane, 100g of ketone solvent-acetone, 100g of ketone solvent-butanone, 100g of high-molecular TPE1475, 50g of high-molecular SBS1401, 80g of MMA grafting monomer, 15g of 2HEMA grafting monomer, 15gAA grafting monomer, 5g of BPO initiator, 6g of BHT terminator, 10g of P710 adhesion promoter, 20g of chlorinated rubber S20 adhesion promoter and 15g of AMS-110 adhesion promoter.
The preparation method is the same as that of example 1.
The solvent and the high polymer matrix TPE/SBS are matched, so that the treating agent has a good treating effect, and bright traces which are difficult to remove are not left after the brushing treating agent is dried. The principle of no trace is that the solubility of the used solvent is relatively weak, the solvent does not belong to a strong solvent, the dissolving capacity of the solvent for the solid matter is general, so that the molecular chain of the solid matter is not completely stretched, the solid content and the viscosity of the treating agent are controlled to be lower, only 3-5 percent and the viscosity is 10-100, so that the coating amount of the treating agent is smaller, the corrosivity of the solvent for the base material is not strong, and the treating agent basically does not leave obvious traces on the base material after being dried by combining various factors.
The embodiments described above are presented to enable those skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications to the present invention based on the disclosure of the present invention within the protection scope of the present invention.
Claims (10)
1. The TPR material surface treating agent is characterized by comprising the following components in parts by weight:
100-1000 parts of alkane solvent, 10-100 parts of butanone solvent, 20-150 parts of polymer matrix to be modified, 30-110 parts of composite vinyl grafting monomer, 1-5 parts of initiator, 2-6 parts of terminator, 15-45 parts of adhesion promoter and 10-100 parts of acetone diluent.
2. The surface treatment agent for TPR material as set forth in claim 1, wherein said polymer matrix comprises 10 to 100 parts of rubber matrix and 10 to 50 parts of resin matrix.
3. The surface treatment agent for TPR material as set forth in claim 2, wherein said rubber matrix is a high molecular TPE 1475.
4. The surface treatment agent for TPR material as set forth in claim 2, wherein the resin matrix is polymer SBS 1401.
5. The surface treatment agent for TPR material as set forth in claim 1, wherein the vinyl-based graft monomer comprises 20 to 80 parts of methacrylic acid graft monomer, 5 to 15 parts of hydroxyethyl methacrylate graft monomer, and 5 to 15 parts of acrylic acid graft monomer.
6. The surface treatment agent for TPR material as set forth in claim 1, wherein the alkane solvent is methylcyclohexane.
7. The surface treatment agent for TPR material as set forth in claim 1, wherein the initiator is dibenzoyl peroxide.
8. The surface treatment agent for TPR material as set forth in claim 1, wherein the terminating agent is dibutylhydroxytoluene.
9. The surface treatment agent for TPR material as set forth in claim 1, wherein the adhesion promoter comprises 5-10 parts of vinyl chloride-vinyl acetate copolymer P710, 5-20 parts of chlorinated rubber S20, and 5-15 parts of multifunctional resin AMS-110.
10. The method for preparing the TPR material surface treatment agent according to any one of claims 1 to 9, comprising the steps of:
s1, mixing an alkane solvent and a butanone solvent, putting the mixture into a water bath, starting stirring, adding a polymer matrix to be modified, and heating to 80-90 ℃ until the solid is completely dissolved;
s2, adding vinyl grafting monomers, adding an initiator, starting to react, keeping the temperature constant at 80-90 ℃, reacting for 4-5 hours, paying attention to the change of the viscosity and the appearance in the whole process, and adding a terminator to terminate after the required viscosity is reached;
s3, cooling to 45-50 ℃, adding the adhesion promoter and the acetone diluent, fully stirring and dissolving for 2 hours, and finishing the whole process to obtain the TPR material surface treating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911415912.4A CN111073012A (en) | 2019-12-31 | 2019-12-31 | TPR material surface treating agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911415912.4A CN111073012A (en) | 2019-12-31 | 2019-12-31 | TPR material surface treating agent and preparation method thereof |
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| CN111073012A true CN111073012A (en) | 2020-04-28 |
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| CN201911415912.4A Pending CN111073012A (en) | 2019-12-31 | 2019-12-31 | TPR material surface treating agent and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175474A (en) * | 2020-10-10 | 2021-01-05 | 南京和润新材料科技有限公司 | Production method of TPR (thermal Plastic rubber) shoe material surface treating agent |
| CN112920292A (en) * | 2021-02-26 | 2021-06-08 | 南宝树脂（佛山）有限公司 | Full-water-based rubber treatment agent for shoe industry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2927631A1 (en) * | 2008-02-15 | 2009-08-21 | Arkema France | USE OF A ADHESION PROMOTER IN A SOLUTION FOR CLEANING THE SURFACE OF A TPE AND / OR PA SUBSTRATE TO INCREASE THE ADHESION OF THE SUBSTRATE WITH AQUEOUS GLUE JOINTS. |
| CN103304750A (en) * | 2012-03-12 | 2013-09-18 | 深圳凯奇化工有限公司 | Production method of TPR shoe material surface treatment agent |
| CN107200985A (en) * | 2016-03-17 | 2017-09-26 | 广东裕田霸力科技股份有限公司 | A kind of rubber surface inorganic agent and its production technology |
| CN109232822A (en) * | 2018-08-21 | 2019-01-18 | 扬州朗劲塑胶实业有限公司 | A kind of TPR shoe material surface treatment agent production method |
-
2019
- 2019-12-31 CN CN201911415912.4A patent/CN111073012A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2927631A1 (en) * | 2008-02-15 | 2009-08-21 | Arkema France | USE OF A ADHESION PROMOTER IN A SOLUTION FOR CLEANING THE SURFACE OF A TPE AND / OR PA SUBSTRATE TO INCREASE THE ADHESION OF THE SUBSTRATE WITH AQUEOUS GLUE JOINTS. |
| CN103304750A (en) * | 2012-03-12 | 2013-09-18 | 深圳凯奇化工有限公司 | Production method of TPR shoe material surface treatment agent |
| CN107200985A (en) * | 2016-03-17 | 2017-09-26 | 广东裕田霸力科技股份有限公司 | A kind of rubber surface inorganic agent and its production technology |
| CN109232822A (en) * | 2018-08-21 | 2019-01-18 | 扬州朗劲塑胶实业有限公司 | A kind of TPR shoe material surface treatment agent production method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175474A (en) * | 2020-10-10 | 2021-01-05 | 南京和润新材料科技有限公司 | Production method of TPR (thermal Plastic rubber) shoe material surface treating agent |
| CN112920292A (en) * | 2021-02-26 | 2021-06-08 | 南宝树脂（佛山）有限公司 | Full-water-based rubber treatment agent for shoe industry |
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Application publication date: 20200428 |
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