CN114276614A - Grafting crosslinking agent for EPDM-PP foaming material and preparation method and application thereof - Google Patents
Grafting crosslinking agent for EPDM-PP foaming material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a graft crosslinking agent for an EPDM-PP (ethylene-propylene-diene monomer) foaming material as well as a preparation method and application thereof. The grafting crosslinking agent for the EPDM-PP foaming material is prepared by reacting an acyl compound A with a dihydric alcohol B to prepare an ABn monomer, wherein n is more than or equal to 2; preparing a graft cross-linking agent with a carboxyl end group by taking a polycarboxyl compound or an anhydride compound as a core through a polyesterification reaction with an ABn monomer; modifying the grafting cross-linking agent with the end group of carboxyl into a vinyl-terminated grafting cross-linking agent with the end group of vinyl through a vinylation reaction; and the number-average relative molecular weight of the vinyl-terminated graft cross-linking agent is controlled to be 500-5000, so that the high-low temperature mechanical property of the EPDM-PP foaming material can be improved, and the fluidity of the material in a molten state can be improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a graft crosslinking agent for an EPDM-PP (ethylene-propylene-diene monomer) foaming material as well as a preparation method and application thereof.
Background
Ethylene propylene diene monomer/polypropylene thermoplastic elastomer (EPDM/PP-TPV) does not contain polar groups, has excellent electrical insulation, is a successfully developed rubber-plastic blended thermoplastic elastomer, and gradually replaces the traditional rubber. The factors influencing the performance of the EPDM/polypropylene thermoplastic elastomer are as follows: rubber-plastic ratio, a vulcanization system, a preparation process and the like. Among them, the vulcanization system is an important factor affecting the EPDM/PP-TPV performance. Different vulcanization systems have different vulcanization mechanisms, and products obtained after dynamic crosslinking have different crosslinking network structures, so that the EPDM/PP-TPV has certain difference in performance.
Such as phenolic resin curing systems: the system only acts on double bonds, has small influence on the resin and is the earliest system. The EPDM/PP-TPV prepared by adopting the phenolic resin vulcanization system has higher melt strength and excellent heat resistance and oil resistance, but the vulcanization process is relatively complex, the product is polluted, the EPDM/PP-TPV is not suitable for preparing light-colored products, the material has strong moisture absorption characteristic, and drying is needed before processing.
A sulfur vulcanization system: the sulfur is cross-linked by connecting different molecular chains together through sulfur bridges formed between polymer molecular chains by monomer sulfur or multi-molecule sulfur. The obtained EPDM/PP-TPV product has good elasticity and high strength, but has the defects of low vulcanization speed, long vulcanization time, high sulfur consumption, easy breakage, large system odor, poor appearance quality of an extruded product and poor processing flowability.
Peroxide cure system: the crosslinking bond is C-C bond, the dynamic vulcanization process is short when a peroxide vulcanization system is adopted, the obtained product has good thermal aging resistance and small compression permanent deformation, but the EPDM dynamic crosslinking can cause PP to be degraded to a certain degree, so that the brittleness of the formed composite material is increased, and the use requirement can not be met.
Therefore, the thermoplastic elastomers prepared by the two other vulcanization systems, except the peroxide vulcanization system, are yellow or deep yellow in natural color, which is not favorable for coloring materials. Furthermore, the three vulcanization systems produce thermoplastic elastomers with poor flow properties at high temperatures. Compared with PP modified without EPDM, the melt index of the modified PP modified by EPDM is greatly reduced. This results in a very limited range of material usage, which is not conducive to injection molding into large and thin-walled parts. Meanwhile, the poor material flow property also increases the energy consumption in the processing process and reduces the working efficiency.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a grafting crosslinking agent for an EPDM-PP foaming material, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the grafting cross-linking agent for the EPDM-PP foaming material is prepared by reacting an acyl compound A with a dihydric alcohol B to prepare an ABn monomer, wherein n is more than or equal to 2; preparing a graft cross-linking agent with an end group of carboxyl by taking a polycarboxyl compound or an anhydride compound as a core through polyesterification reaction with an ABn monomer; modifying the grafting cross-linking agent with the end group of carboxyl into a vinyl-terminated grafting cross-linking agent with the end group of vinyl through a vinylation reaction; and the number average molecular weight of the vinyl-terminated graft cross-linking agent is controlled within 500-5000.
Further, the amide compound A is trimellitic anhydride amide and trimellitic anhydride chloride.
Further, the dihydric alcohol B is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, ethylene glycol, 1, 4-dimethylolcyclohexane or 1, 4-dimethylolbenzene.
Further, the polycarboxyl compound is at least one of phthalic acid, terephthalic acid, isophthalic acid and trimellitic acid; the acid anhydride compound is at least one of phthalic anhydride and trimellitic anhydride.
The preparation method of the grafting crosslinking agent for the EPDM-PP foaming material comprises the following steps:
s1, adding the acyl compound A and the dihydric alcohol B into a reactor filled with an organic solvent for reaction to obtain an ABn monomer, wherein n is more than or equal to 2;
s2, adding a polycarboxyl compound or an anhydride compound and an organic solvent into a reactor, and carrying out polyesterification reaction with an ABn monomer to obtain a graft cross-linking agent with a carboxyl end group;
s3, adding a vinylation raw material into the reactor for reaction to obtain a graft cross-linking agent with a vinyl end group;
s4, after the reaction is finished, removing the organic solvent in vacuum to obtain a vinyl-terminated graft cross-linking agent; wherein the temperature of the vacuum desolventizing agent is controlled to be 80-120 ℃, and the vacuum degree is controlled to be 0.01-0.08 MPa.
Further, in the step S1, the molar ratio of the acyl compound A to the dihydric alcohol B is 1-2.2: 1; the reaction temperature is 80-150 ℃, and the reaction time is 2-3 hours.
Further, in the step S2, the molar ratio of the polycarboxyl compound or the anhydride compound to the ABn monomer is 1: 2-8, the reaction temperature is 80-250 ℃, and the reaction time is 3-8 hours.
Further, in step S3, the mole number of the vinylation raw material is equal to the mole number of the carboxyl group in the graft cross-linking agent molecule with the terminal group being carboxyl group, the reaction temperature is controlled at 60-150 ℃, and the reaction time is controlled at 1-3 hours.
Furthermore, the total amount of the organic solvent used in the steps S1 and S2 is 20-80% of the total weight of the acyl compound A and the dihydric alcohol B, and the vinylation raw material is glycidyl acrylate or glycidyl methacrylate.
The graft cross-linking agent is used for preparing EPDM-PP foaming material.
The invention has the beneficial effects that: as can be seen from the above description of the present invention, compared with the prior art, the graft cross-linking agent for EPDM-PP foaming material of the present invention is prepared by reacting acyl compound A and dihydric alcohol B to prepare ABn monomer, wherein n is not less than 2; preparing a graft cross-linking agent with a carboxyl end group by taking a polycarboxyl compound or an anhydride compound as a core through a polyesterification reaction with an ABn monomer; modifying the grafting cross-linking agent with the end group of carboxyl into a vinyl-terminated grafting cross-linking agent with the end group of vinyl through a vinylation reaction; and the number-average relative molecular weight of the vinyl-terminated graft crosslinking agent is controlled to be 500-5000, so that the high-low temperature mechanical property of the EPDM-PP foaming material can be improved, and the fluidity of the material in a molten state can be improved.
Detailed Description
The technical solutions in the present invention will be described clearly and completely below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "connected" and "connected" are to be interpreted broadly, e.g., as being either fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In the preferred embodiment of the invention, the grafting cross-linking agent for the EPDM-PP foaming material is prepared by reacting an acyl compound A with a dihydric alcohol B to prepare an ABn monomer, wherein n is more than or equal to 2; preparing a graft crosslinking agent with a carboxyl end group by taking a polycarboxyl compound or an anhydride compound as a core through a polyesterification reaction with an ABn monomer; modifying the grafting cross-linking agent with the end group of carboxyl into a vinyl-terminated grafting cross-linking agent with the end group of vinyl through a vinylation reaction; and the number average molecular weight of the vinyl-terminated graft cross-linking agent is controlled within 500-5000.
As a preferred embodiment of the present invention, it may also have the following additional technical features: the amide compound A is trimellitic anhydride amide and trimellitic anhydride acyl chloride; the dihydric alcohol B is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, diethylene glycol, 1, 4-dimethylolcyclohexane or 1, 4-dimethylolbenzene; the polycarboxyl compound is at least one of phthalic acid, terephthalic acid, isophthalic acid and trimellitic acid; the acid anhydride compound is at least one of phthalic anhydride and trimellitic anhydride.
Example 1
Adding 1 mol part of trimellitic anhydride amide and 1 mol part of 1, 4-butanediol into a reactor filled with 30mL of tetrahydrofuran solution, stirring, heating to 80 ℃, reacting at the temperature for 2 hours, adding 0.25 mol part of phthalic acid and 200mL of dimethylbenzene, heating to the dimethylbenzene reflux temperature, reacting at the temperature until water separation formed by polycondensation is complete, adding 0.5 mol part of acrylic acid glycidyl ester after the reaction is finished, continuing to react at the dimethylbenzene reflux temperature for 3 hours, and recovering the solvent under the conditions of 0.01MPa of vacuum degree and 80 ℃ under reduced pressure to obtain the light brown viscous vinyl-terminated graft crosslinking agent.
Example 2
Adding 1 mol part of trimellitic anhydride chloride and 1.5 mol parts of 1, 4-butanediol into a reactor filled with 30mL of N, N' -dimethylformamide solution, starting stirring, heating to 100 ℃, reacting at the temperature for 2.5 hours, adding 0.25 mol part of terephthalic acid and 200mL of dimethylbenzene, heating to the dimethylbenzene reflux temperature, reacting at the temperature until water separation formed by polycondensation is complete, adding 0.5 mol part of glycidyl methacrylate after the reaction is finished, continuously reacting at the dimethylbenzene reflux temperature for 6 hours, and decompressing and recovering the solvent under the condition that the vacuum degree is 0.04MPa and the temperature is 100 ℃ to obtain the light brown vinyl-terminated graft cross-linking agent.
Example 3
Adding 1 mol part of trimellitic anhydride acyl chloride and 2.2 mol parts of 1, 4-dimethylolcyclohexane into a reactor filled with 30mL of xylene solution, stirring, heating to 150 ℃, reacting at the temperature for 3 hours, adding 0.25 mol part of trimellitic acid and 200mL of xylene, heating to the reflux temperature of toluene, reacting at the temperature until water separation formed by polycondensation is complete, after the reaction is finished, adding 0.75 mol part of glycidyl methacrylate, continuing to react at the reflux temperature of xylene for 8 hours, and recovering the solvent under reduced pressure at the vacuum degree of 0.08MPa and 120 ℃ to obtain the light brown viscous vinyl-terminated graft cross-linking agent.
Preparation of EPDM-PP foaming material
According to the materials and the using amounts listed in the table 1, a mixture formed by mixing additives such as ethylene propylene diene monomer EPDM, polypropylene PP, stearic acid, zinc oxide, antioxidant and the like is put into an internal mixer to be pressurized to 6 kilograms and kneaded for 15 minutes, cold water is rapidly filled for cooling when the temperature reaches 150 ℃, a vinyl-terminated graft crosslinking agent, vulcanizing agent dicumyl peroxide (DCP), triallyl isocyanurate (TAIC) and a foaming agent are added when the temperature is reduced to 100 ℃, kneading is carried out for 5 minutes, and the materials are discharged after being fully mixed and dissolved to obtain a rubber compound; then carrying out hot refining in an open mill, and controlling the temperature at 110 ℃; discharging the slices by a slice discharging machine, and controlling the temperature at 90 ℃; finally, foaming, cold cutting and shaping in a die to obtain the EPDM-PP foaming material
The formulation proposed in the comparative example is similar to the formulation proposed in the examples, but without the addition of the vinyl-terminated graft cross-linking agent, and the following data are given by weight.
TABLE 1 examples and comparative examples of EPDM-PP foamed Material materials and amounts (parts)
The vinyl-terminated graft crosslinking agent in example 4 was the vinyl-terminated graft crosslinking agent prepared in example 1 of the present invention, the vinyl-terminated graft crosslinking agent in example 5 was the vinyl-terminated graft crosslinking agent prepared in example 2 of the present invention, and the vinyl-terminated graft crosslinking agent in example 6 was the vinyl-terminated graft crosslinking agent prepared in example 3 of the present invention.
The EPDM-PP foaming material sample prepared by the method is subjected to mechanical property test, and the test results are listed in Table 2.
TABLE 2 mechanical Properties of EPDM-PP foamed Material
The EPDM-PP foaming material prepared by the invention has the advantages of large elongation at break, low temperature resistance, aging resistance, strong impact resistance, low compression set and the like; and each formula can enable each effective component to be well compatible and blended, and the price is low, thereby meeting the new requirements of industrial development. Meanwhile, the preparation method is simple and feasible and is suitable for industrial production.
The above additional technical features can be freely combined and used in superposition by those skilled in the art without conflict.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. The grafting crosslinking agent for the EPDM-PP foaming material is characterized in that: reacting an acyl compound A with dihydric alcohol B to prepare an ABn monomer, wherein n is more than or equal to 2; preparing a graft cross-linking agent with a carboxyl end group by taking a polycarboxyl compound or an anhydride compound as a core through a polyesterification reaction with an ABn monomer; modifying the grafting cross-linking agent with the end group of carboxyl into a vinyl-terminated grafting cross-linking agent with the end group of vinyl through a vinylation reaction; and the number average molecular weight of the vinyl-terminated graft cross-linking agent is controlled within 500-5000.
2. Graft crosslinking agent for EPDM-PP foams according to claim 1, characterized in that: the amide compound A is trimellitic anhydride amide and trimellitic anhydride acyl chloride.
3. Graft crosslinking agent for EPDM-PP foams according to claim 1, characterized in that: the dihydric alcohol B is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, monoethylene glycol, 1, 4-dimethylolcyclohexane or 1, 4-dimethylolbenzene.
4. Graft crosslinking agent for EPDM-PP foams according to claim 1, characterized in that: the polycarboxyl compound is at least one of phthalic acid, terephthalic acid, isophthalic acid and trimellitic acid; the acid anhydride compound is at least one of phthalic anhydride and trimellitic anhydride.
5. The preparation method of the grafting crosslinking agent for the EPDM-PP foaming material is characterized by comprising the following steps: graft-crosslinking agent for EPDM-PP foams according to any of claims 1 to 4, obtained by:
s1, adding the acyl compound A and the dihydric alcohol B into a reactor filled with an organic solvent for reaction to obtain an ABn monomer, wherein n is more than or equal to 2;
s2, adding a polycarboxyl compound or an anhydride compound and an organic solvent into a reactor, and carrying out polyesterification reaction with an ABn monomer to obtain a graft cross-linking agent with a carboxyl end group;
s3, adding a vinylation raw material into the reactor for reaction to obtain a graft cross-linking agent with a vinyl end group;
s4, after the reaction is finished, removing the organic solvent in vacuum to obtain a vinyl-terminated graft cross-linking agent; wherein the temperature of the vacuum desolventizing agent is controlled to be 80-120 ℃, and the vacuum degree is controlled to be 0.01-0.08 MPa.
6. The process for the preparation of graft-crosslinking agent for EPDM-PP foams according to claim 5, characterized in that: in the step S1, the molar ratio of the acyl compound A to the dihydric alcohol B is 1-2.2: 1; the reaction temperature is 80-150 ℃, and the reaction time is 2-3 hours.
7. The process for the preparation of graft-crosslinking agent for EPDM-PP foams according to claim 5, characterized in that: in the step S2, the molar ratio of the polycarboxyl compound or the anhydride compound to the ABn monomer is 1: 2-8, the reaction temperature is 80-250 ℃, and the reaction time is 3-8 hours.
8. The process for the preparation of graft-crosslinking agent for EPDM-PP foams according to claim 5, characterized in that: in the step S3, the mole number of the vinylation raw material is equal to the mole number of the carboxyl in the grafting cross-linking agent with the end group of the carboxyl, the reaction temperature is controlled to be 60-150 ℃, and the reaction time is controlled to be 1-3 hours.
9. The process for the preparation of graft-crosslinking agent for EPDM-PP foams according to claim 5, characterized in that: the total amount of the organic solvent used in the steps S1 and S2 is 20-80% of the total weight of the acyl compound A and the dihydric alcohol B, and the vinylation raw material is glycidyl acrylate or glycidyl methacrylate.
10. Use of the graft crosslinking agent for EPDM-PP foams according to any of claims 1 to 4 for the preparation of EPDM-PP foams.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014672A (en) * | 2004-09-09 | 2007-08-08 | 关西涂料株式会社 | Thermosetting aqueous coating composition |
| CN104419101A (en) * | 2013-08-23 | 2015-03-18 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene graft microcellular foaming material and preparation method thereof |
| CN110204835A (en) * | 2019-05-24 | 2019-09-06 | 武汉金发科技有限公司 | A kind of toughening agent composition and a kind of thermoplas tic resin composite and preparation method thereof |
| CN110256660A (en) * | 2019-05-27 | 2019-09-20 | 武汉金发科技有限公司 | A kind of hyper-branched polyester and its synthetic method and a kind of thermoplastic resin composition and preparation method thereof |
| WO2021200716A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
-
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- 2021-12-24 CN CN202111594205.3A patent/CN114276614A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101014672A (en) * | 2004-09-09 | 2007-08-08 | 关西涂料株式会社 | Thermosetting aqueous coating composition |
| CN104419101A (en) * | 2013-08-23 | 2015-03-18 | 上海杰事杰新材料(集团)股份有限公司 | Polypropylene graft microcellular foaming material and preparation method thereof |
| CN110204835A (en) * | 2019-05-24 | 2019-09-06 | 武汉金发科技有限公司 | A kind of toughening agent composition and a kind of thermoplas tic resin composite and preparation method thereof |
| CN110256660A (en) * | 2019-05-27 | 2019-09-20 | 武汉金发科技有限公司 | A kind of hyper-branched polyester and its synthetic method and a kind of thermoplastic resin composition and preparation method thereof |
| WO2021200716A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
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