WO2013155961A1

WO2013155961A1 - Ethylene-propylene-diene monomer grafted maleic anhydride and preparation method therefor

Info

Publication number: WO2013155961A1
Application number: PCT/CN2013/074291
Authority: WO
Inventors: 周兵
Original assignee: 深圳市科聚新材料有限公司
Priority date: 2012-04-19
Filing date: 2013-04-17
Publication date: 2013-10-24
Also published as: CN102643391B; CN102643391A

Abstract

Disclosed are an ethylene-propylene-diene monomer grafted maleic anhydride and a preparation method therefor, wherein the ethylene-propylene-diene monomer grafted maleic anhydride comprises the following formulation components in weight percentages: 95% - 97% of ethylene-propylene-diene monomer, 0.1% - 0.2% of an initiator, 1% - 2% of maleic anhydride, 0.8% - 1.5% of a styrene monomer, and 0.2% - 0.5% of hexamethylphosphoric triamine. The present invention uses the ethylene-propylene-diene monomer as a grafting substrate and maleic anhydride as a grafting monomer, and performs the graft under the action of the initiator during melt extrusion. The grafting ratio and the grafting efficiency thereof are high, and the product has little odour, white colour, and is environmentally friendly and safe. The preparation method therefor has a simple process, easily controllable conditions, and is suitable for industrial production.

Description

EPDM rubber grafted maleic anhydride and preparation method thereof

The invention belongs to the technical field of polymer materials, and particularly relates to an ethylene propylene diene rubber grafted maleic anhydride and a preparation method thereof.

Background technique

Ethylene Propylene Diene Monomer (EPDM) is a terpolymer of ethylene, propylene and non-conjugated diene. It has good resistance to oxidation, ozone, low temperature, impact resistance and thermal stability. Advantages, blending with engineering plastics, can greatly improve the impact strength and low temperature resistance of engineering plastics, but EPDM itself is non-polar, and has poor compatibility with polar plastics such as polyamide and polyester. In order to improve EPDM The compatibility with these polar plastics often requires the grafting of polar groups to EPDM. Among them, maleic anhydride (MAH) is the most widely used one.

The graft modification of EPDM mainly includes two methods: solution grafting and melt grafting. The grafting method of EPDM is used to graft MAH with EPDM. The grafting reaction time is long, the grafting efficiency is low, and a large amount of toxic and flammable solvents are consumed. The production cost is high, the damage to the human body is large, the environment is polluted, and the land occupation is large, and it is difficult to achieve continuous operation. The existing EPDM obtained by the melt grafting method has a rich odor, a low color whiteness and a low grafting ratio, thereby limiting the application of the EPDM.

Summary of the invention

Provided is an ethylene propylene diene rubber grafted maleic anhydride comprising the following weight percentages of the formulation components:

EPDM 94 - 97%

Initiator 0.1 ~ 0.4%

Maleic anhydride 1 ~ 3%

Styrene monomer 0.5 ~ 3%

Hexamethylphosphoric acid triamine 0.1 ~ 0.8%.

And the method for preparing the above ethylene propylene diene rubber grafted maleic anhydride comprises the following steps: respectively, weighing each component according to the above formula components;

Dissolving the initiator in the component in the styrene monomer in the component to obtain a first solution; adding the components other than the initiator and the styrene monomer to the first solution to obtain a mixture Material

The mixture was melt extruded and pelletized to obtain an ethylene propylene diene monomer grafted maleic anhydride. According to the ethylene-propylene propylene rubber grafted maleic anhydride of the present invention, ethylene propylene diene rubber is used as a graft base, maleic anhydride is a graft monomer, and grafting is carried out under the action of an initiator during melt extrusion. The grafting rate and grafting efficiency are high, the product has low odor and white color. Moreover, the ethylene-propylene propylene rubber grafted maleic anhydride does not contain harmful substances, and is environmentally safe. The preparation method of the ethylene propylene diene rubber grafted maleic anhydride according to the invention only needs to mix the components according to the formula and melt-graft and extrude to obtain the ethylene propylene rubber grafted maleic anhydride, and gives three The high grafting rate of ethylene-propylene rubber grafted maleic anhydride, the preparation method is simple, the conditions are easy to control, the cost is low, the equipment requirements are low, and it is suitable for industrial production.

DRAWINGS

The invention will be further described with reference to the accompanying drawings and embodiments. Fig. 1 is a schematic view showing the process flow of the preparation method of the ethylene propylene diene rubber grafted maleic anhydride according to the embodiment of the present invention.

detailed description

In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below with reference to the embodiments and drawings.

The embodiment of the invention provides a grafted maleic anhydride of ethylene propylene diene with high grafting rate, small odor and white color. The EPDM grafted maleic anhydride comprises the following weight percentages of the formulation components:

EPDM 94 - 97%

Initiator 0.1 ~ 0.4%

Maleic anhydride 1 ~ 3%

Styrene monomer 0.5 ~ 3%

Hexamethylphosphoric acid triamine 0.1 ~ 0.8%.

The EPDM grafted maleic anhydride is grafted with ethylene propylene diene monomer, maleic anhydride is grafted monomer, grafted under the action of initiator during melt extrusion, graft ratio and The grafting efficiency is high, the odor is small, the color is white, and the specific performance parameters are shown in Table 1 below.

Among them, the styrene monomer can effectively inhibit the copolymerization and cross-linking between the molecules of MAH itself, so that the grafting reaction between the molecules of EPDM and MAH is sufficient; the hexamethylene phosphate triamine is the electron donor, in the melting During the grafting reaction, it supplies electrons and electrons to the cationic intermediate, and terminates the chain growth, thereby inhibiting the polymerization of the cations, thereby effectively inhibiting the crosslinking reaction between the components and increasing the grafting ratio. . Therefore, in the melt extrusion process, the styrene monomer and the hexamethylphosphoric acid triamine can effectively prevent the occurrence of side reactions such as copolymerization and crosslinking, and increase the graft ratio of the ethylene propylene diene monomer grafted maleic anhydride. Through the graft modification of EPDM with maleic anhydride, the polarity of EPDM itself is effectively improved, its compatibility with polar plastics such as polyamide and polyester is improved, and EPDM rubber is added. The application range of grafted maleic anhydride.

Preferably, the above ethylene propylene diene rubber is preferably an ethylene propylene diene rubber having a Mooney viscosity of 40 to 80, such as an ethylene propylene diene rubber of the brand number 4725P manufactured by Dow Chemical Co., Ltd. having a Mooney viscosity of 60, and the weight thereof is 100%. The content of the fraction is preferably 95 to 96%. The preferred Mooney viscosity ethylene propylene diene monomer is used as a graft base to effectively balance the fluidity and toughness of the ethylene propylene diene monomer grafted maleic anhydride. The above initiator is preferably bis-(tert-butylperoxyisopropyl)benzene (BIPB), such as the commercial brand No. 14S-FL manufactured by AkzoNobel, preferably in a weight percentage of 0.2 to 0.3%. The bis-(tert-butylperoxyisopropyl)benzene can be decomposed to generate free radicals under the condition of grafting reaction, and can effectively promote the production of free radicals in the ethylene propylene diene rubber molecular chain and graft with maleic anhydride. The graft ratio was increased, as in the case of Examples 1 and 2 below, the graft ratio was as high as 1.42%, and the grafting efficiency was also as high as 81.7%. Of course, other initiators in the art, such as dicumyl peroxide (DCP), can also be used as the initiator. However, the inventors found that the use of other initiators, such as DCP, reduced the grafting efficiency of EPDM to maleic anhydride to 67.5%, the grafting rate to 0.81%, and the maleic anhydride residue. Large, high cross-linking rate. Moreover, the finished product of the ethylene propylene diene monomer grafted maleic anhydride has a yellowish color and the odor of the material is increased.

The above maleic anhydride is preferably present in an amount of from 1.5 to 2.5% by weight. Maleic anhydride is a colorless needle crystal with a strong polarity, such as maleic anhydride produced by Haichang Wind Co., Ltd. After grafting maleic anhydride with non-polar EPDM rubber, the strong polar side group is introduced into the ethylene dipropylene rubber main chain, thereby enhancing the ethylene propylene rubber grafted maleic anhydride. The compatibility of the materials with other polar plastics makes the other polar plastics more evenly and finely dispersed, greatly improving their blending and vulcanization mechanical properties.

The weight percentage of the above styrene monomer is preferably from 1 to 2%. The styrene monomer is a colorless, oil-like liquid with a special aroma, and an industrial grade styrene monomer produced by Maoming Petrochemical can be used. During the grafting process, it can inhibit the copolymerization and cross-linking between MAH molecules, so that the grafting reaction between the molecules of EPDM and MAH is sufficient. When the styrene monomer was contained in Example 1, the graft ratio of the ethylene propylene diene monomer grafted maleic anhydride was as high as 0.98%, and the grafting efficiency was as high as 81.7%. When the styrene monomer was not contained, the graft ratio of the ethylene propylene diene monomer grafted maleic anhydride was only 0.72%, and the grafting efficiency was only 60%, as in Comparative Example 2.

The above hexamethylphosphoric acid triamine preferably has a weight percentage of 0.2 to 0.5%. The hexamethylphosphoric acid triamine is a colorless transparent liquid, and an analytical grade of hexamethylene phosphate triamine such as that produced by Shanghai Minglong Chemical Co., Ltd. can be used. During the grafting process, it is possible to effectively inhibit the crosslinking reaction between the components and increase the grafting ratio, see Examples 1, 2 and Comparative Example 3.

Further, based on the above examples, the above ethylene propylene diene rubber grafted maleic anhydride may further comprise the following weight percent of the formulation components:

Antioxidant 0.2 ~ 0.4%, and / or

Other additives 0.5 ~ 1%.

Preferably, the above antioxidant is a compound having a mass ratio of 2:1 as a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is tetra[β-(3,5-di-tert-butyl-4) -Hydroxyphenyl)propionic acid] pentaerythritol ester, the secondary antioxidant is phenyl tris(2,4-di-tert-butyl) phosphite. The antioxidant component can effectively improve the oxidation resistance of the EPDM grafted maleic anhydride of the present embodiment and prolong its service life. Tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate]pentaerythritol ester as main antioxidant and tris(2,4-di-tert-butyl) sub-as a secondary antioxidant Phenyl phosphate can be produced by Ciba The brands IrganoxlOlO and Irganoxl68. The preferred antioxidant has a better effect on the oxidation resistance of the ethylene propylene diene monomer grafted maleic anhydride. Of course, if the oxidation resistance of the ethylene propylene diene rubber grafted maleic anhydride of the present embodiment is relatively low, other antioxidants in the art can also be used.

Other auxiliaries mentioned above include lubricants and/or processing aids. Among them, processing aids include thermal stabilizers. The lubricant component can be a lubricant commonly used in the art. It can adhere to the surface of other components during the melt extrusion process, so that the components are sufficiently dispersed, so that the performance of the ethylene propylene diene grafted maleic anhydride of the present embodiment is stable. The processing properties associated with the grafting of maleic anhydride of EPDM rubber can be improved by adding a type of processing aid, such as a thermal stabilizer, as needed.

The embodiment of the invention further provides a method for preparing the above-mentioned ethylene propylene diene rubber grafted maleic anhydride, and the process flow thereof is shown in FIG. 1 . The method comprises the following steps:

501. Weighing the formulation components: weigh each component according to the above-mentioned ethylene-propylene rubber grafted maleic anhydride formulation component;

502. preparing a first solution: dissolving the initiator in the component weighed in step S01 in the styrene monomer in the component;

503. preparing a mixture material: the components other than the initiator and the styrene monomer in the component weighed in step S01, such as ethylene propylene diene monomer, maleic anhydride, hexamethylene phosphate, etc. (according to The formulation component may further include an antioxidant, other auxiliary agent, etc.) added to the first solution prepared in step S02 to obtain a mixed material;

504. Melt extrusion: The mixed material in the step S03 is melt-extruded and granulated to obtain an ethylene propylene diene monomer grafted maleic anhydride.

Specifically, in the above step S01, the formulation and the content and the kind of each component in the formula of the ethylene propylene diene rubber grafted maleic anhydride are as described above, and in order to save space, no further details are provided herein.

In the above step S02, during the process of dissolving the initiator in the styrene monomer, the stirring may be slowed until the initiator is completely dissolved, so that the two are thoroughly mixed.

In the above step S03, when the remaining components are added to the first solution, in order to make the components sufficiently mixed, the components may be mixed in a mixer.

In the above step S04, the mixture is melt extruded and extruded through a twin-screw extruder. By controlling the extrusion time and temperature, the components in the EPDM grafted maleic anhydride formulation are melted, and the initiator generates free radicals, thereby causing the occurrence of ethylene propylene diene rubber and maleic anhydride. Graft modification. Wherein, during the extrusion process, the temperature of each section of the mixture in the twin-screw extruder is preferably: a zone temperature of 140 to 145 ° C, a zone temperature of 140 to 150 ° C, and a zone temperature of 150 to 160 °. C, four zones temperature 145 ~ 155 °C, head 150 ~ 160 °C; screw speed 240 ~ 20 r / min, residence time 3 ~ 6min, pressure 12 ~ 18MPa. The preferred melt grafting temperature and time can increase the grafting efficiency and grafting ratio of the ethylene propylene diene monomer to maleic anhydride. The preparation method of the above-mentioned ethylene propylene diene rubber grafted maleic anhydride only needs to mix the components according to the formula and extrude and granulate at an appropriate temperature and time to obtain a product, in the melt extrusion process, Under the action of the initiator, the graft modification between the ethylene propylene diene rubber and the maleic anhydride is initiated, and the ethylene propylene glycol grafted maleic anhydride material with high grafting rate is obtained, and the EPDM is given. The rubber-grafted maleic anhydride material has a small odor and a white color. The preparation method has the advantages of simple process, easy control of conditions, low cost, low requirements on equipment, and is suitable for industrial production. In addition, the components of the formula are safe and non-toxic, and contact with the human body will not cause harm to the human body, and is safe and environmentally friendly.

The present invention will now be further described in detail by taking the formulation and preparation method of specific EPDM and maleic anhydride as examples.

In the formulations of EPDM and maleic anhydride in the following examples, the percentage of each component is a percentage by weight. EPDM uses Mooney viscosity 60 (produced by The Dow Chemical Company, product grade 4725P), BIPB uses analytical grade (produced by AkzoNobel, product grade 14S-FL), and maleic anhydride uses industrial grade colorless needle crystal structure. (produced by Shanghai Changfeng Co., Ltd.), styrene monomer used in industrial grade (Maoming Petrochemical production), hexamethylenephosphoric acid triamine selected analytical grade (produced by Shanghai Minglong Chemical Co., Ltd.), antioxidant is four [β - (3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester and phenyl (3,4-di-tert-butyl) phosphite complex (produced by Ciba, the product grades are IrganoxlOlO, and Irganoxl68).

Example 1

An ethylene propylene diene monomer grafted maleic anhydride having a weight percent formulation component as shown in Table 1 below.

The preparation method is as follows:

The styrene monomer is weighed into a container at a weight ratio of 1%, BIPB 0.15% is dissolved in the styrene monomer, stirred evenly, and then EPDM 96.25%, maleic anhydride 1.2%, hexamethylenephosphoric acid triamine 0.4 %, 1010/168 0.2/0.1%, 0.7% of other processing aids are weighed, pour into the stirrer, slowly add the styrene/BIPB mixed solution prepared in front to the material, and mix well. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded and granulated. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140 °C; two zones: 150 °C; three zones: 160 °C; four zones: 150 °C; head: 160 °C; 280, residence time 3 ~ 6min, pressure 15MPa.

Example 2

The preparation method is as follows:

The styrene monomer is weighed into a container at a weight ratio of 1%, BIPB 0.15 % is dissolved in the styrene monomer, stirred and hooked, and then EPDM 95.65%, maleic anhydride 1.8%, hexamethylenephosphoric acid triamine 0.4 %, 1010/168 0.2/0.1 %, 0.7% of other processing aids are weighed, pour into the stirrer, slowly add the previously prepared styrene/BIPB mixed solution to the material, stir Evenly. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded and granulated. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140 °C; two zones: 150 °C; three zones: 160 °C; four zones: 150 °C; head: 160 °C; 280, residence time 3 ~ 6min, pressure 15MPa.

Example 3

The preparation method is as follows:

Pour styrene into a container, BIPB is dissolved in styrene monomer, stir and hook, then EPDM, maleic anhydride, hexamethylphosphoric acid triamine is poured into the blender, and the front styrene/BIPB is mixed. The solution was slowly added dropwise to the material and stirred. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded and granulated. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 145 °C; two zones: 150 °C; three zones: 150 °C; four zones: 155 °C; head: 160 °C; 320, residence time 3 min, pressure 18 MPa.

Example 4

EPDM 96%, BIPB 0.2%, styrene monomer 1%, maleic anhydride 1.5%, hexamethylene triamine 0.3%, antioxidant 1010 0.1%, antioxidant 168 0.1%, heat stabilizer 0.8% .

The preparation method is as follows:

Pour styrene into a container, BIPB is dissolved in styrene monomer, stirred and hooked, and then EPDM, maleic anhydride, hexamethylphosphoric acid triamine, 1010/168, heat stabilizer is poured into the mixer, the front The prepared styrene/BIPB mixed solution is slowly added dropwise to the material and stirred. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded and granulated. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140 °C; two zones: 150 °C; three zones: 160 °C; four zones: 150 °C; head: 160 °C; 240, residence time 6min, pressure 12MPa.

Comparative example 1

The preparation method is as follows:

The styrene monomer is 1% by weight, and is poured into the container. DCP 0.15 % is dissolved in the styrene monomer, stirred evenly, and then EPDM 96.25 %, maleic anhydride 1.2 %, hexamethylene sulfonate Amine 0.4%, 1010/168 0.2/0.1%, the other 0.7% is weighed, pour into the stirrer, slowly add the previously prepared styrene/BIPB mixed solution to the material, stir and hook. The mixed material is added to the hopper of the twin-screw extruder, grafted by melt reaction, and extruded. Granules. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140 °C; two zones: 150 °C; three zones: 160 °C; four zones: 150 °C; head: 160 °C; 280, residence time 3 ~ 6min, pressure 15MPa.

Comparative example 2

The preparation method is as follows:

The BIPB was 0.15% by weight, 97.25% by weight of EPDM, 1.2% of maleic anhydride, 0.4% of hexamethylphosphoric acid triamide 0.4%, 1010/1680.2/0.1%, and the other 0.7% was weighed, poured into a stirrer, and stirred. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded and granulated. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140. C; Zone 2: 150 ° C; Zone 3: 160 ° C; Zone 4: 150 ° C; Head: 160 ° C; Screw speed 280, Residence time 3 ~ 6 min, pressure 15 MPa.

Comparative example 3

The preparation method is as follows:

The styrene monomer is 1% by weight, and is poured into the container. BIPB 0.15% is dissolved in the styrene monomer, stirred and hooked, and then EPDM 96.65%, maleic anhydride 1.2%, 1010/1680.2/0.1 %, other 0.7% is good, pour into the blender, slowly add the styrene/BIPB mixed solution prepared in front to the material, stir and hook. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded and granulated. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140°C; two zones: 150°C; three zones: 160°C; four zones: 150°C; head: 160°C; 280, residence time 3 ~ 6min, pressure 15MPa.

Comparative example 4

The preparation method is as follows:

The styrene monomer is weighed into a container at a weight ratio of 1%, BIPB 0.15% is dissolved in the styrene monomer, stirred evenly, and then EPDM 96.25%, maleic anhydride 1.2%, hexamethylenephosphoric acid triamine 0.4 %, 1010/1680.2/0.1%, other 0.7% is good, pour into the stirrer, slowly add the styrene/BIPB mixed solution prepared in front to the material, stir and hook. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded and granulated. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140°C; two zones: 150°C; three zones: 160°C; four zones: 150°C; head: 160°C; 200 r/min, residence time Ί ~ lOmin, pressure 15 MPa. Comparative example 5

The preparation method is as follows:

The styrene monomer is weighed into a container at a weight ratio of 1%, BIPB 0.15% is dissolved in the styrene monomer, stirred evenly, and then EPDM 96.25%, maleic anhydride 1.2%, hexamethylenephosphoric acid triamine 0.4 % , 1010/1680.2/0.1%, other 0.7% is good, pour into the stirrer, slowly add the styrene/BIPB mixed solution prepared in front to the material, stir and hook. The mixed material is added to a hopper of a twin-screw extruder, grafted by a melt reaction, and extruded into pellets. Among them, the temperature setting of each heating zone of the screw is: one zone temperature: 140 °C; two zones: 150 °C; three zones: 160 °C; four zones: 150 °C; head: 160 °C; 360 r/min, residence time l ~ 3min, pressure 15MPa.

Performance Testing:

The grafting ratio and grafting efficiency of the ethylene propylene terephthalate grafted maleic anhydride prepared in the above Examples 1 to 2 and Comparative Example 1 to Comparative Example 5 were tested by acid-base titration. The test results are shown in the table. 1. In addition, the graft ratio and grafting efficiency of the ethylene propylene diene rubber grafted maleic anhydride prepared in the above Examples 3 and 4 are close to the grafting ratio and grafting efficiency of the examples, and in addition, the ethylene propylene diene monomer rubber The grafted maleic anhydride has a low odor and a white color.

Table 1

It can be seen from the above Table 1 that the grafting efficiency and grafting ratio of the grafted maleic anhydride of EPDM rubber prepared in Example 1 and Example 2 were both high, wherein the grafting efficiency reached 81.7% and 78.9, respectively. %, the grafting rate is 0.98% and 1.42%, respectively, and the odor is 4艮, which achieves the requirement of low odor, and the color is white. When blended with other engineering plastics, it does not affect the color of the final product. The grafting efficiencies of Examples 3 and 4 were 74.4% and 75.3%, respectively, the grafting efficiency was high, the grafting ratio was high, the odor of Example 3 was small, and Example 4 was smaller, all of which met the requirements of low odor. In terms of color, the color of Example 4 was white, and the effect was very good, while the color of Example 3 was slightly yellowish, mainly because of the absence of the addition of an antioxidant, which caused the material to partially degrade and oxidize.

In Comparative Example 1, after converting BIPB to DCP, the graft ratio of the material was 0.81, the grafting efficiency was decreased to 67.5%, and the color was yellow, the material odor was serious, the maleic anhydride residue was large, and the crosslinking rate was higher. high. It can be seen that the graft ratio, grafting efficiency, odor and finished color of the EPDM grafted maleic anhydride prepared by the choice of initiator are relatively large, and the ternary prepared by the BIPB initiator is used. The related properties of ethylene-propylene rubber grafted maleic anhydride are much better than those of other initiators.

Comparing Example 2 with Example 1, the grafting efficiency was reduced from 81.7% to 60% without adding styrene monomer, and the styrene monomer inhibited the copolymerization of maleic anhydride in the formulation, and was effective after the addition. Preventing the copolymerization of maleic anhydride and improving the grafting efficiency of the material.

Comparing Example 3 with Example 1, the grafting efficiency of the material decreased with the addition of hexamethylene-based triamine, from 81.7% to 68.3%. In the formulation, the additive hexamethylene-based triamine To inhibit the crosslinking of the material, during the melt grafting reaction, the hexamethylphosphoric acid triamine is an electron donor, electrons are given to the cationic intermediate, and the chain growth is terminated to inhibit the polymerization of the cation.

Comparing Example 4 with Example 1, when the screw rotation speed was decreased from 280 to 200, the melt grafting reaction time was too long, rising from 3 to 6 minutes to 7 to 10 minutes, the material grafting efficiency was decreased, and the crosslinking ratio of the material was increased. , the color turns yellow.

Comparing Example 5 with Example 1, the screw rotation speed increased from 280 to 360, and the material melt grafting reaction time became shorter, from 3 to 6 minutes to 1-3 minutes, the grafting efficiency of the material decreased significantly, and many maleic anhydride also In the future, it will be grafted onto EPDM.

It can be seen from the above analysis that the ethylene propylene diene rubber grafted maleic anhydride according to the present invention and the preparation method thereof use ethylene propylene diene rubber as a graft base and maleic anhydride as a graft monomer, which is in the process of melt extrusion. Grafting under the action of initiator, high grafting rate and grafting efficiency, small odor, color white, environmental protection and safety. The preparation method is simple in process, easy to control, low in cost, low in equipment requirements, and suitable for industrial production. It effectively overcomes the existing grafting method for the grafting of EPDM. The grafting reaction in the MAH has a long grafting reaction time, low grafting efficiency, large consumption of toxic and flammable solvents, and high production cost.

The above is only the preferred embodiment of the present invention, and is only used to help the understanding of the present invention and is not intended to limit the present invention. Variations to the above-described embodiments may be made by those skilled in the art in light of the teachings herein.

Claims

Rights request

An ethylene propylene diene monomer grafted maleic anhydride characterized by comprising the following components by weight:

EPDM 94 - 97%

Initiator

maleic anhydride

Styrene monomer

Hexamethylphosphoric acid triamine 0.1 ~ 0.8%.

2. The ethylene propylene diene rubber grafted maleic anhydride according to claim 1, which is characterized by comprising the following weight percentage of the formulation component:

EPDM 95 - 96 %

Initiator 0.2 ~ 0.3 ° /

Maleic anhydride 1.5 - 2.5°/

The ethylene propylene diene rubber grafted maleic anhydride according to claim 1 or 2, wherein the initiator is bis-(tert-butylperoxyisopropyl)benzene.

The ethylene propylene diene rubber grafted maleic anhydride according to claim 1 or 2, wherein the ethylene propylene diene monomer has a Mooney viscosity of 40 to 80.

The ethylene propylene diene rubber grafted maleic anhydride according to claim 1 or 2, which further comprises the following weight percentage of the formulation component:

Antioxidant 0.2 ~ 0.4%.

The ethylene propylene diene monomer grafted maleic anhydride according to claim 5, wherein the antioxidant is a compound having a mass ratio of 2: 1 as a main antioxidant and a secondary antioxidant. , wherein the main antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid] pentaerythritol ester, and the auxiliary antioxidant is tris( ² , ⁴ _ di-tert-butyl) Phenyl phosphate.

7. The ethylene propylene diene rubber grafted maleic anhydride according to claim 5, characterized by further comprising the following weight percentage of the formulation component:

Lubricant and / or processing aid 0.5 ~ 1%.

A method for preparing an ethylene propylene diene monomer grafted maleic anhydride, comprising the steps of:

The formulation component according to any one of claims 1 to 7, respectively, weigh each component; the initiator in the component is dissolved in the styrene monomer in the component to obtain a first solution;

Adding other components of the component other than the initiator and the styrene monomer to the first solution to obtain a mixture; The mixture was melt extruded and granulated to obtain the ethylene propylene diene monomer grafted maleic anhydride.

9. The method for preparing ethylene propylene diene rubber grafted maleic anhydride according to claim 8, wherein: the extrusion is extrusion using a twin-screw extruder, and the mixture is in the double The temperature of each section in the screw extruder is: one zone temperature 140~ 145 °C, two zone temperature 140~ 150 °C, three zone temperature 150~160 °C, four zone temperature 145 ~ 155 °C, head 150 ~ 160 °C; screw speed 240 ~ 320 r / min, residence time 3 ~ 6min, pressure 12 ~ 18MPa.