CN115595107A - Polishing-free EVA (ethylene vinyl acetate) treating agent and preparation method thereof - Google Patents
Polishing-free EVA (ethylene vinyl acetate) treating agent and preparation method thereof Download PDFInfo
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- CN115595107A CN115595107A CN202211260803.1A CN202211260803A CN115595107A CN 115595107 A CN115595107 A CN 115595107A CN 202211260803 A CN202211260803 A CN 202211260803A CN 115595107 A CN115595107 A CN 115595107A
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- treating 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a polishing-free EVA (ethylene vinyl acetate) treating agent and a preparation method thereof, belonging to the field of shoe treating agents. The formula of the anti-aging coating comprises ethyl acetate, sec-butyl acetate, EVA365 particles, TPU particles, fumaric acid, benzoyl peroxide, methyl methacrylate, an anti-aging agent BHT, styrene-butadiene-styrene (styrene-butadiene-styrene) resin and chlorinated rubber. The preparation method comprises the steps of mixing, graft copolymerization, modification and solid content adjustment. The polishing-free EVA treating agent prepared by the invention is particularly suitable for the EVA sole processing process of a polishing-free procedure; the invention does not contain organic solvents such as toluene, butanone and the like, thereby greatly reducing the production of VOC; and the initial viscosity, the peel strength and other properties can be greatly improved.
Description
Technical Field
The invention belongs to the technical field of shoe treating agents, and particularly relates to a polishing-free EVA treating agent and a preparation method thereof.
Background
With the rapid development of the shoe industry, EVA (ethylene-vinyl acetate copolymer) foam materials are used in large quantities for sole materials, especially midsoles of sneakers and beach slippers. However, since EVA is a weak polar material in a high polymer, there is no good affinity with a chloroprene rubber adhesive and a polyurethane adhesive having strong polarity, which brings difficulty to the adhesion of EVA. In order to improve the adhesion between the shoe material and the EVA foam material, it is common practice to use a processor for bonding. Commercially available common treatment agents are those in which active ingredients are dissolved by acetone, butanone, cyclohexanone, ethyl acetate, toluene, n-hexane, and the like, and these solvent-type treatment agents account for 95% or more of the total amount of commercially available treatment agents, and the solvent content of these treatment agents is mostly 90% or more.
According to statistics, the VOC (volatile organic compounds) generated by the shoe treating agent in China is nearly 9 million tons per year, and the influence of the volatile organic compounds volatilized into the atmosphere is immeasurable. The common EVA treating agent pollutes the environment due to volatility during use, and organic solvents originally sealed inside are further released during a polishing step; prolonged contact has adverse consequences on the physical health of the operator, as well as a lasting negative impact on the environment.
Disclosure of Invention
The invention provides a polishing-free EVA (ethylene vinyl acetate) treating agent and a preparation method thereof, which can reduce the generation of VOC (volatile organic compounds).
The invention aims to provide a polishing-free EVA (ethylene vinyl acetate) treating agent which comprises the following components in parts by mass:
68-70 parts of ethyl acetate
8.53-10 of sec-butyl acetate
EVA365 granule 5-6.75
TPU granules 5.95 to 6.25
Fumaric acid 1-1.5
Benzoyl peroxide 1.73-1.95
Methyl methacrylate 2.84-2.91
0.35-0.45 of antioxidant BHT
Phenylmaleimide resin 1-2
0.3-0.5 parts of chlorinated rubber.
In particular, the EVA365 particles are dupont usa.
In particular, the TPU particles are basf.
The second purpose of the invention is to provide a preparation method of the sanding-free EVA treating agent, which comprises the following steps:
(1) Mixing and stirring ethyl acetate and sec-butyl acetate, adding EVA365 particles and TPU particles, and dissolving to obtain a mixture A;
(2) Adding fumaric acid into the mixture A, and stirring to obtain a mixture B;
(3) Sequentially adding benzoyl peroxide and methyl methacrylate into the mixture B for graft copolymerization to obtain a mixture C; the reaction is terminated until the infrared spectrum of the mixture C does not change any more;
(4) And cooling the mixture C, adding an anti-aging agent BHT, and stirring to obtain a semi-finished product.
(5) And adding ethyl acetate, coumarone resin and chlorinated rubber into the semi-finished product, and stirring until the solid content is within the range of 4.4 +/-0.4%, thereby obtaining the EVA treating agent.
Particularly, in the step (1), ethyl acetate and sec-butyl acetate are mixed, and the stirring speed is more than or equal to 400rpm; the temperature is more than or equal to 50 ℃, and the stirring time is more than or equal to 10min.
Particularly, in the step (1), the stirring speed is more than or equal to 150rpm, and the dissolving time is 2.5-3h.
Particularly, in the step (2), the stirring speed is more than or equal to 80rpm; the temperature is more than or equal to 60 ℃, and the stirring time is 30-36min.
Particularly, in the step (3), the temperature of the graft copolymerization reaction is more than or equal to 85 ℃, and the reaction time is 4-5h.
Particularly, in the step (4), the temperature is reduced to be less than or equal to 40 ℃, the anti-aging agent BHT is added, the stirring is carried out for 30-36min, and the stirring speed is more than or equal to 80rpm, so as to obtain a semi-finished product.
Particularly, in the step (5), the stirring speed is more than or equal to 400rpm; stirring for 30-36min.
According to the invention, the EVA and the TPU are grafted, the EVA section in the macromolecular copolymer is similar to and compatible with the EVA vamp, and the isocyanate insert block can play a role in bonding materials after surface treatment, so that the polishing-free EVA is pretreated, and the material surface is favorably used as a bridge before being glued so as to be bonded with the PU glue.
Compared with the prior art, the invention has the beneficial effects that:
the polishing-free EVA treating agent prepared by the invention is particularly suitable for the EVA sole processing process of a polishing-free procedure; the invention does not contain organic solvents such as toluene, butanone and the like, thereby greatly reducing the production of VOC; and the initial viscosity, the peel strength and other properties can be greatly improved.
Detailed Description
For a better understanding of the present invention, the present invention is further described in conjunction with the following specific examples, wherein the terminology used in the examples is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
In the invention:
BPO refers to benzoyl peroxide;
TPU refers to thermoplastic polyurethane elastomers;
EVA refers to ethylene-vinyl acetate copolymer;
MMA means methyl methacrylate;
HDI refers to hexamethylene diisocyanate;
the EVA365 particles are from dupont, usa.
The TPU granules are from Pasfu, germany.
A preparation method of a polishing-free EVA treating agent comprises the following steps:
(1) Weighing corresponding raw materials according to the mass parts in the table 1 for later use;
(2) Mixing and stirring ethyl acetate and sec-butyl acetate, adding EVA365 particles and TPU particles, and dissolving to obtain a mixture A;
the speed, temperature, time of mixing and stirring; the time of dissolution is shown in table 1.
(3) Adding fumaric acid into the mixture A, and stirring to obtain a mixture B;
the mixing and stirring rate, temperature and time are shown in Table 1.
(4) Sequentially adding benzoyl peroxide and methyl methacrylate into the mixture B for graft copolymerization to obtain a mixture C; when the viscosity of the mixture C begins to become thick continuously, sampling and beating an infrared spectrum once every half hour, and when the infrared spectrum does not change any more and the stirring of a glass rod is in a wiredrawing shape, judging that the reaction is terminated;
the temperature and reaction time of the graft copolymerization are shown in Table 1.
(5) And cooling the mixture C, adding an anti-aging agent BHT, and stirring to obtain a semi-finished product.
The temperature of the cooling and the stirring time after the antioxidant BHT was added are shown in Table 1.
(6) And adding ethyl acetate, coumarone resin and chlorinated rubber into the semi-finished product, and stirring until the solid content is within the range of 4.4 +/-0.4%, thereby obtaining the EVA treating agent.
The rotation speed and the stirring time of the stirring are shown in Table 1.
TABLE 1
The adhesion strength test was performed on the finished products of examples 1-5 in table 1 with a commercially available EVA treatment under the following conditions: and testing a sample wafer with the thickness of 2cm multiplied by 20cm, standing for 10 minutes after the material is pasted, testing the initial tension, standing for 24 hours, testing the later tension, and testing by using a high-speed rail servo tension tester. The results are shown in table 2 below.
TABLE 2
The above detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but rather the scope of the invention is intended to include all equivalent implementations or modifications without departing from the scope of the invention.
Claims (8)
1. The polishing-free EVA treating agent is characterized by comprising the following components in parts by mass:
68-70 parts of ethyl acetate
8.53-10 of sec-butyl acetate
EVA365 granule 5-6.75
TPU granules 5.95 to 6.25
Fumaric acid 1-1.5
Benzoyl peroxide 1.73-1.95
Methyl methacrylate 2.84-2.91
0.35-0.45 of antioxidant BHT
Phenylmaleimide resin 1-2
0.3-0.5 parts of chlorinated rubber.
2. The preparation method of the sanding-free EVA treating agent of claim 1, which is characterized by comprising the following steps:
(1) Mixing and stirring ethyl acetate and sec-butyl acetate, adding EVA365 particles and TPU particles, and dissolving to obtain a mixture A;
(2) Adding fumaric acid into the mixture A, and stirring to obtain a mixture B;
(3) Sequentially adding benzoyl peroxide and methyl methacrylate into the mixture B for graft copolymerization to obtain a mixture C; the reaction is terminated until the infrared spectrum of the mixture C does not change any more;
(4) And cooling the mixture C, adding an anti-aging agent BHT, and stirring to obtain a semi-finished product.
(5) And adding ethyl acetate, coumarone resin and chlorinated rubber into the semi-finished product, and stirring until the solid content is within the range of 4.4 +/-0.4%, thereby obtaining the EVA treating agent.
3. The preparation method of the sanding-free EVA treating agent of claim 2, wherein in the step (1), the ethyl acetate and the sec-butyl acetate are mixed, and the stirring speed is not less than 400rpm; the temperature is more than or equal to 50 ℃, and the stirring time is more than or equal to 10min.
4. The preparation method of the sanding-free EVA treating agent of claim 2, wherein in the step (1), the stirring speed is not less than 150rpm, and the dissolving time is 2.5-3h.
5. The preparation method of the sanding-free EVA treating agent of claim 2, wherein in the step (2), the stirring speed is not less than 80rpm; the temperature is more than or equal to 60 ℃, and the stirring time is 30-36min.
6. The preparation method of the sanding-free EVA treating agent of claim 2, wherein in the step (3), the graft copolymerization reaction temperature is not less than 85 ℃, and the reaction time is 4-5h.
7. The preparation method of the sanding-free EVA treating agent of claim 2, wherein in the step (4), the temperature is reduced to 40 ℃ or lower, the anti-aging agent BHT is added, and the mixture is stirred for 30-36min at a stirring speed of 80rpm or higher to obtain a semi-finished product.
8. The preparation method of the sanding-free EVA treating agent of claim 2, wherein in the step (5), the stirring speed is not less than 400rpm; stirring for 30-36min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211260803.1A CN115595107B (en) | 2022-10-14 | 2022-10-14 | Polishing-free EVA (ethylene-vinyl acetate copolymer) treating agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211260803.1A CN115595107B (en) | 2022-10-14 | 2022-10-14 | Polishing-free EVA (ethylene-vinyl acetate copolymer) treating agent and preparation method thereof |
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| CN115595107A true CN115595107A (en) | 2023-01-13 |
| CN115595107B CN115595107B (en) | 2023-06-16 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037725A (en) * | 1988-05-18 | 1989-12-06 | 成都科技大学 | Multifunctional adhesive for shoes |
| CN103619944A (en) * | 2011-06-23 | 2014-03-05 | 尤尼吉可株式会社 | Aqueous dispersion, and laminate, adhesive for footwear, and footwear made using same |
| US20150174877A1 (en) * | 2013-12-20 | 2015-06-25 | ZakLad Produkcji Obuwia "LEMIGO" | Method of Connecting Elements made of Foamed Ethylene Copolymer and Vinyl Acetate EVA with Polyurethane |
| CN105623357A (en) * | 2014-10-30 | 2016-06-01 | 江苏冠军涂料科技集团有限公司 | High-grade industrial paint special-purpose eco-friendly diluent |
| CN113402837A (en) * | 2021-06-02 | 2021-09-17 | 佛山市高明大都化工有限公司 | EVA (ethylene-vinyl acetate) treating agent and preparation method thereof |
| CN113969091A (en) * | 2021-11-03 | 2022-01-25 | 全叶娟 | Water-based EVA (ethylene-vinyl acetate) treating agent and preparation method thereof |
-
2022
- 2022-10-14 CN CN202211260803.1A patent/CN115595107B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037725A (en) * | 1988-05-18 | 1989-12-06 | 成都科技大学 | Multifunctional adhesive for shoes |
| CN103619944A (en) * | 2011-06-23 | 2014-03-05 | 尤尼吉可株式会社 | Aqueous dispersion, and laminate, adhesive for footwear, and footwear made using same |
| US20150174877A1 (en) * | 2013-12-20 | 2015-06-25 | ZakLad Produkcji Obuwia "LEMIGO" | Method of Connecting Elements made of Foamed Ethylene Copolymer and Vinyl Acetate EVA with Polyurethane |
| CN105623357A (en) * | 2014-10-30 | 2016-06-01 | 江苏冠军涂料科技集团有限公司 | High-grade industrial paint special-purpose eco-friendly diluent |
| CN113402837A (en) * | 2021-06-02 | 2021-09-17 | 佛山市高明大都化工有限公司 | EVA (ethylene-vinyl acetate) treating agent and preparation method thereof |
| CN113969091A (en) * | 2021-11-03 | 2022-01-25 | 全叶娟 | Water-based EVA (ethylene-vinyl acetate) treating agent and preparation method thereof |
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| CN115595107B (en) | 2023-06-16 |
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