CN111363234B - Degradable EVA (ethylene-vinyl acetate) foam material and preparation method thereof - Google Patents
Degradable EVA (ethylene-vinyl acetate) foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a degradable EVA (ethylene-vinyl acetate) foaming material and a preparation method thereof, wherein the degradable EVA foaming material is prepared from the following raw materials in parts by weight: 35-45 parts of ethylene-vinyl acetate copolymer, 15-20 parts of POE (polyolefin elastomer), 8-12 parts of rubber, 6-10 parts of bio-based poly (pentanediaminyl adipate) polymer, 20-30 parts of degradable organic matter, 1-1.5 parts of stearic acid, 1-1.2 parts of zinc oxide, 1-1.5 parts of peroxide and 1-5 parts of AC (alternating current) foaming agent; the degradable organic matter is cassava flour or corn starch; the vinyl acetate content in the ethylene-vinyl acetate copolymer is 32.5-36.5%; the POE elastomer is a mixture of ethylene-octene copolymer and ethylene-hexene copolymer. The degradable EVA foaming material has good wear resistance; has high elasticity; the portability is good; has good anti-slip effect; has good mechanical property; the comprehensive performance is good, and the application prospect is wide.
Description
Technical Field
The invention relates to the technical field of foaming materials, in particular to a degradable EVA foaming material and a preparation method thereof.
Background
Ethylene-vinyl acetate copolymer (EVA) is a rubber-like thermoplastic having excellent flexibility, low-temperature brain flexibility, elasticity, stress crack resistance, and good plasticity and processability, compared to polyethylene, and thus is widely used. The EVA cross-linked foaming material has excellent physical property and no toxicity, and has the advantages of low density, high specific strength, capacity of absorbing load, etc. owing to the existence of gas phase. However, the EVA foaming material has the defects of large deformation, insufficient wear resistance, slipping and low-temperature hardening, thereby limiting the application of the EVA foaming material.
In recent years, the research on EVA cross-linked foaming materials at home and abroad is more, the formula and the processing technology are mainly involved, and the addition of a modifier is an important way for the formula. Among them, thermoplastic polymers such as thermoplastic rubber, ethylene propylene diene monomer and the like are commonly used as modifiers for EVA crosslinking foaming.
However, the currently used EVA foam has the following problems:
1. the wear resistance is poor;
2. the elasticity is poor;
3. the anti-slip effect is poor;
4. non-degradable, non-environmental friendly, and poor comprehensive performance such as mechanical strength.
Disclosure of Invention
Based on the above situation, the present invention aims to provide a degradable EVA foam material and a preparation method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a degradable EVA foaming material is prepared from the following raw materials in parts by weight:
35 to 45 portions of ethylene-vinyl acetate copolymer,
15-20 parts of POE elastomer,
8 to 12 portions of rubber,
6-10 parts of bio-based poly (glutaric adipamide),
20 to 30 portions of degradable organic matter,
1 to 1.5 portions of stearic acid,
1 to 1.2 portions of zinc oxide,
1 to 1.5 portions of peroxide,
1-5 parts of AC foaming agent.
Preferably, the degradable organic matter is cassava flour or corn starch.
Preferably, the content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 32.5-36.5%.
Preferably, the POE elastomer is a mixture of an ethylene-octene copolymer and an ethylene-hexene copolymer.
Preferably, the bio-based polyhexamethylene diamine adipate polymer is made from petroleum-based adipic acid and bio-based 1, 5-pentanediamine.
Preferably, the peroxide is a mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene.
Preferably, the degradable EVA foaming material is prepared from the following raw materials in parts by weight:
40 parts of ethylene-vinyl acetate copolymer,
17.5 parts of POE elastomer,
10 portions of rubber,
8 parts of bio-based poly (glutaric adipamide) polymer,
25 portions of degradable organic matter,
1.3 parts of stearic acid,
1.1 parts of zinc oxide,
1.25 parts of peroxide,
And 2.5 parts of an AC foaming agent.
Preferably, the mass ratio of the ethylene-octene copolymer to the ethylene-hexene copolymer in the mixture of the ethylene-octene copolymer and the ethylene-hexene copolymer is 1: (0.3-0.4).
Preferably, the content of octene in the ethylene-octene copolymer is 30-35%; the hexene content in the ethylene-hexene copolymer is 32-38%.
Preferably, the rubber is natural rubber.
Preferably, the mass ratio of the tin peroxide to the bis (tert-butylperoxyisopropyl) benzene in the mixture of the tin peroxide and the bis (tert-butylperoxyisopropyl) benzene is 1: (0.22-0.26).
The invention also provides a preparation method of the degradable EVA foaming material, which comprises the following steps:
A. respectively weighing ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent;
B. feeding ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matters, stearic acid, zinc oxide, peroxide and an AC foaming agent into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the degradable EVA foaming material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the degradable EVA foaming material is prepared by selecting raw materials, optimizing the content of each raw material, and selecting ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matters, stearic acid, zinc oxide, peroxide and AC foaming agent in proper proportion, so that the advantages of the degradable EVA foaming material are fully exerted, the degradable organic matters complement and promote each other, the quality of the product is improved, and the prepared degradable EVA foaming material has good wear resistance; the rebound rate is high, the compression permanent deformation is small, and the elasticity is high; the density is small, the weight per unit volume is light, and the portability is good; the dry type slip coefficient and the wet type slip coefficient are high, the slip performance is good, and the slip effect is good; the tensile strength is high, and the mechanical property is good; the comprehensive performance is good, and the application prospect is wide.
DIN wear resistance test of the degradable EVA foaming material shows that the degradable EVA foaming material has good wear resistance, and compared with a comparative example, the degradable EVA foaming material has high wear resistance and is close to the wear resistance of the comparative example on the premise of not adding a wear-resistant agent; the density is small, the weight per unit volume is light, and the portability is good; the degradable EVA foam material has high rebound rate, small compression set and high elasticity, and compared with a comparative example, the degradable EVA foam material has the advantages that the rebound rate is obviously improved, the compression set is smaller, namely the elasticity is better; compared with the comparative example, the degradable EVA foaming material has the advantages that the dry type slip coefficient and the wet type slip coefficient are both obviously improved, and the slip effect is obviously improved; compared with a comparative example, the degradable EVA foaming material has the advantages that the tensile strength is obviously higher than that of the comparative example under the condition that the density is close, namely the foaming degree is close, and the mechanical property is better.
The degradable EVA foaming material is prepared by adding ethylene-vinyl acetate copolymer, POE elastomer, rubber and bio-based poly (glutaric adipate) diamine polymer in a proper proportion into the raw materials, and the raw materials are used as composite base materials which are matched with each other to play a good synergistic effect, so that the degradable EVA foaming material has good wear resistance; has high elasticity; the portability is good; has good anti-slip effect; and has good mechanical properties;
the degradable EVA foaming material is prepared by adding POE elastomer and rubber in proper proportion into raw materials, wherein the POE elastomer is preferably a mixture of ethylene-octene copolymer and ethylene-hexene copolymer; the rubber is preferably natural rubber. The preferable POE elastomer is mainly used for improving the elasticity of the degradable EVA foaming material and improving the anti-slip effect of the degradable EVA foaming material to a certain degree; the preferable rubber is mainly used for improving the anti-slip effect of the degradable EVA foaming material, the elasticity of the degradable EVA foaming material is improved to a certain extent, the preferable rubber and the preferable rubber are matched with each other to play a good synergistic effect, the elasticity and the anti-slip effect of the degradable EVA foaming material are greatly improved, the resilience rate of the degradable EVA foaming material is high, the compression set is small, the degradable EVA foaming material has high elasticity, and compared with a comparative example, the resilience rate of the degradable EVA foaming material is obviously improved, the compression set is smaller, and the elasticity is better; compared with the comparative example, the degradable EVA foaming material has the advantages that the dry type slip coefficient and the wet type slip coefficient are both obviously improved, and the slip effect is obviously improved.
The degradable EVA foaming material is prepared by adding a proper proportion of bio-based poly (pentanediamine adipate) polymer and a degradable organic matter into raw materials, wherein the bio-based poly (pentanediamine adipate) polymer is preferably prepared from petroleum-based adipic acid and bio-based 1, 5-pentanediamine; the degradable organic matter is preferably cassava flour or corn starch. In the raw material system of the invention, the preferable bio-based poly (pentanediamine adipate) polymer and the degradable organic matter are mutually crosslinked and matched with other components to obtain a good elastic crosslinking network, thereby ensuring that the degradable EVA foaming material has good wear resistance; has high elasticity; the portability is good; has good anti-slip effect; and has good mechanical properties; the degradable EVA foaming material has good degradability; the addition of the bio-based poly (pentanediamine adipate) polymer in a proper proportion greatly improves the wear resistance and mechanical property of the degradable EVA foaming material.
The degradable EVA foaming material of the invention is added with peroxide in proper proportion, and the peroxide is preferably a mixture of tin peroxide and bis (tert-butylperoxyisopropyl) benzene. In the raw material system, the preferable peroxide can enable the ethylene-vinyl acetate copolymer, the POE elastomer, the rubber, the bio-based poly (glutaric adipate) diamine polymer, the degradable organic matter and the like to have good crosslinking effect, so that a good elastic crosslinking network is obtained, and the degradable EVA foaming material has good wear resistance; has high elasticity; the portability is good; has good anti-slip effect; and has good mechanical properties.
The degradable EVA foaming material can be produced by screw extrusion, has simple process and simple and convenient operation, and saves manpower and equipment cost.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are either commercially available from conventional sources or are prepared in conventional manners.
Example 1:
a degradable EVA foaming material is prepared from the following raw materials in parts by weight:
35 to 45 portions of ethylene-vinyl acetate copolymer,
15-20 parts of POE elastomer,
8 to 12 portions of rubber,
6-10 parts of bio-based poly (glutaric adipamide),
20 to 30 portions of degradable organic matter,
1 to 1.5 portions of stearic acid,
1 to 1.2 portions of zinc oxide,
1 to 1.5 portions of peroxide,
1-5 parts of an AC foaming agent.
In this embodiment, the degradable organic substance is preferably tapioca or corn starch.
In this embodiment, the content of vinyl acetate in the ethylene-vinyl acetate copolymer is preferably 32.5 to 36.5%.
In this example, the POE elastomer is preferably a mixture of an ethylene-octene copolymer and an ethylene-hexene copolymer.
In this embodiment, the bio-based polypentamethyleneadipamide polymer is preferably made from petroleum-based adipic acid and bio-based 1, 5-pentanediamine.
In this embodiment, the peroxide is preferably a mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene.
In this embodiment, the degradable EVA foaming material is preferably made from the following raw materials in parts by weight:
40 parts of ethylene-vinyl acetate copolymer,
17.5 parts of POE elastomer,
10 portions of rubber,
8 parts of bio-based poly (glutaric adipamide) polymer,
25 portions of degradable organic matter,
1.3 parts of stearic acid,
1.1 parts of zinc oxide,
1.25 parts of peroxide,
And 2.5 parts of an AC foaming agent.
In this embodiment, the mass ratio of the ethylene-octene copolymer and the ethylene-hexene copolymer in the mixture of the ethylene-octene copolymer and the ethylene-hexene copolymer is preferably 1: (0.3-0.4).
In this embodiment, the octene content of the ethylene-octene copolymer is preferably 30 to 35%; the hexene content in the ethylene-hexene copolymer is preferably 32 to 38%.
In this embodiment, the rubber is preferably natural rubber.
In this embodiment, the mass ratio of tin peroxide to bis (t-butylperoxyisopropyl) benzene in the mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene is preferably 1: (0.22-0.26).
The embodiment also provides a preparation method of the degradable EVA foaming material, which includes the following steps:
A. respectively weighing ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent;
B. feeding ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matters, stearic acid, zinc oxide, peroxide and an AC foaming agent into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the degradable EVA foaming material.
Example 2:
a degradable EVA foaming material is prepared from the following raw materials in parts by weight:
35 parts of ethylene-vinyl acetate copolymer,
15 portions of POE elastomer,
8 portions of rubber,
6 parts of bio-based poly (pentanediaminadipate) polymer,
20 portions of degradable organic matter,
1 part of stearic acid,
1 part of zinc oxide,
1 part of peroxide,
And 1 part of AC foaming agent.
In this embodiment, the degradable organic substance is tapioca or corn starch.
In this example, the vinyl acetate content of the ethylene-vinyl acetate copolymer was 32.5%.
In this example, the POE elastomer was a mixture of ethylene-octene copolymer and ethylene-hexene copolymer.
In this example, the bio-based polyhexamethylene diamine adipate polymer was made from petroleum-based adipic acid and bio-based 1, 5-pentanediamine.
In this example, the peroxide is a mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene.
In this example, the mass ratio of the ethylene-octene copolymer and the ethylene-hexene copolymer in the mixture of the ethylene-octene copolymer and the ethylene-hexene copolymer was 1:0.3.
in this example, the ethylene-octene copolymer had an octene content of 30%; the hexene content in the ethylene-hexene copolymer was 32%.
In this example, the rubber is natural rubber.
In this embodiment, the mass ratio of tin peroxide to bis (t-butylperoxyisopropyl) benzene in the mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene is 1:0.22.
in this embodiment, the preparation method of the degradable EVA foam material includes the following steps:
A. respectively weighing ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent;
B. feeding ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediamine adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the degradable EVA foaming material.
Example 3:
a degradable EVA foaming material is prepared from the following raw materials in parts by weight:
45 parts of ethylene-vinyl acetate copolymer,
20 parts of POE elastomer,
12 portions of rubber,
10 parts of bio-based poly (glutaric adipamide) polymer,
30 portions of degradable organic matter,
1.5 parts of stearic acid,
1.2 parts of zinc oxide,
1.5 parts of peroxide,
And 5 parts of an AC foaming agent.
In this embodiment, the degradable organic substance is tapioca or corn starch.
In this embodiment, the vinyl acetate content of the ethylene-vinyl acetate copolymer is 36.5%.
In this example, the POE elastomer was a mixture of ethylene-octene copolymer and ethylene-hexene copolymer.
In this example, the bio-based polyhexamethylene diamine adipate polymer was made from petroleum-based adipic acid and bio-based 1, 5-pentanediamine.
In this example, the peroxide is a mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene.
In this example, the mass ratio of the ethylene-octene copolymer and the ethylene-hexene copolymer in the mixture of the ethylene-octene copolymer and the ethylene-hexene copolymer was 1:0.4.
in this example, the ethylene-octene copolymer had an octene content of 35%; the hexene content in the ethylene-hexene copolymer was 38%.
In this example, the rubber is natural rubber.
In this embodiment, the mass ratio of tin peroxide to bis (t-butylperoxyisopropyl) benzene in the mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene is 1:0.26.
in this embodiment, the preparation method of the degradable EVA foam material includes the following steps:
A. respectively weighing ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent;
B. feeding ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediamine adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the degradable EVA foaming material.
Example 4:
a degradable EVA foaming material is prepared from the following raw materials in parts by weight:
40 parts of ethylene-vinyl acetate copolymer,
17.5 parts of POE elastomer,
10 parts of rubber,
8 parts of bio-based poly (glutaric adipamide) polymer,
25 portions of degradable organic matter,
1.3 parts of stearic acid,
1.1 parts of zinc oxide,
1.25 parts of peroxide,
And 2.5 parts of an AC foaming agent.
In this embodiment, the degradable organic substance is tapioca flour or corn starch.
In this example, the vinyl acetate content of the ethylene-vinyl acetate copolymer was 34.5%.
In this example, the POE elastomer was a mixture of ethylene-octene copolymer and ethylene-hexene copolymer.
In this example, the bio-based polyhexamethylene diamine adipate polymer was made from petroleum-based adipic acid and bio-based 1, 5-pentanediamine.
In this example, the peroxide is a mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene.
In this example, the mass ratio of the ethylene-octene copolymer and the ethylene-hexene copolymer in the mixture of the ethylene-octene copolymer and the ethylene-hexene copolymer was 1:0.35.
in this example, the ethylene-octene copolymer had an octene content of 32.5%; the hexene content in the ethylene-hexene copolymer was 35%.
In this example, the rubber is natural rubber.
In this embodiment, the mass ratio of tin peroxide to bis (t-butylperoxyisopropyl) benzene in the mixture of tin peroxide and bis (t-butylperoxyisopropyl) benzene is 1:0.24.
in this embodiment, the preparation method of the degradable EVA foam includes the following steps:
A. respectively weighing ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent;
B. feeding ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matters, stearic acid, zinc oxide, peroxide and an AC foaming agent into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the degradable EVA foaming material.
Comparative example:
chinese patent publication No. CN 110577696A.
The following tests on the degradable EVA foams obtained in examples 2 to 4 of the present invention and comparative routine performance are shown in Table 1.
TABLE 1
As can be seen from the above table, the degradable EVA foam material of the present invention has the following advantages:
DIN abrasion resistance tests show that the degradable EVA foaming material has good abrasion resistance, and compared with a comparative example, the degradable EVA foaming material has high abrasion resistance and is close to the abrasion resistance of the comparative example on the premise of not adding an abrasion-resistant agent; the density is small, the weight per unit volume is light, and the portability is good; the degradable EVA foam material has high rebound rate, small compression set and high elasticity, and compared with a comparative example, the degradable EVA foam material has the advantages that the rebound rate is obviously improved, the compression set is smaller, and the elasticity is better; compared with the comparative example, the degradable EVA foaming material has the advantages that the dry type slip coefficient and the wet type slip coefficient are both obviously improved, and the slip effect is obviously improved; compared with the comparative example, the degradable EVA foaming material has the advantages that the tensile strength is obviously higher than that of the comparative example under the condition that the densities are close, namely the foaming degrees are close, and the degradable EVA foaming material has better mechanical property.
The above are only preferred embodiments of the present invention, and it should be noted that the above preferred embodiments should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (1)
1. The degradable EVA foaming material is characterized by being prepared from the following raw materials in parts by weight:
40 parts of ethylene-vinyl acetate copolymer, 17.5 parts of POE (polyolefin elastomer), 10 parts of rubber, 8 parts of bio-based poly (pentanediamine adipate) polymer, 25 parts of degradable organic matter, 1.3 parts of stearic acid, 1.1 parts of zinc oxide, 1.25 parts of peroxide and 2.5 parts of AC (alternating current) foaming agent;
the degradable organic matter is cassava flour or corn starch, the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 32.5-36.5%, the POE elastomer is a mixture of an ethylene-octene copolymer and an ethylene-hexene copolymer, and the mass ratio of the ethylene-octene copolymer to the ethylene-hexene copolymer in the mixture of the ethylene-octene copolymer and the ethylene-hexene copolymer is 1: (0.3-0.4), the content of octene in the ethylene-octene copolymer is 30-35%, and the content of hexene in the ethylene-hexene copolymer is 32-38%;
the bio-based poly (pentanediamine adipate) polymer is prepared from petroleum-based adipic acid and bio-based 1, 5-pentanediamine, and the rubber is natural rubber;
the peroxide is a mixture of tin peroxide and bis (tert-butylperoxyisopropyl) benzene, and the mass ratio of the tin peroxide to the bis (tert-butylperoxyisopropyl) benzene in the mixture of the tin peroxide and the bis (tert-butylperoxyisopropyl) benzene is 1: (0.22-0.26);
the preparation method of the degradable EVA foaming material comprises the following steps:
A. respectively weighing ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediaminyl adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent;
B. feeding ethylene-vinyl acetate copolymer, POE elastomer, rubber, bio-based poly (pentanediamine adipate) polymer, degradable organic matter, stearic acid, zinc oxide, peroxide and AC foaming agent into a double-screw extruder, and carrying out melt extrusion and granulation to obtain the degradable EVA foaming material.
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| CN112933557A (en) * | 2021-02-03 | 2021-06-11 | 天长市正牧铝业科技有限公司 | High-sealing-performance PU (polyurethane) veneered football with butyl liner and preparation process of football |
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