WO2013155961A1 - Polymère d'éthylène-propylène-diène greffé anhydride maléique et procédé de préparation correspondant - Google Patents

Polymère d'éthylène-propylène-diène greffé anhydride maléique et procédé de préparation correspondant Download PDF

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Publication number
WO2013155961A1
WO2013155961A1 PCT/CN2013/074291 CN2013074291W WO2013155961A1 WO 2013155961 A1 WO2013155961 A1 WO 2013155961A1 CN 2013074291 W CN2013074291 W CN 2013074291W WO 2013155961 A1 WO2013155961 A1 WO 2013155961A1
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maleic anhydride
ethylene propylene
propylene diene
grafted maleic
grafting
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PCT/CN2013/074291
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English (en)
Chinese (zh)
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周兵
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深圳市科聚新材料有限公司
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Publication of WO2013155961A1 publication Critical patent/WO2013155961A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers

Definitions

  • 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.
  • Ethylene Propylene Diene Monomer 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.
  • MAH maleic anhydride
  • 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.
  • an ethylene propylene diene rubber grafted maleic anhydride comprising the following weight percentages of the formulation components:
  • 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;
  • the mixture was melt extruded and pelletized to obtain an ethylene propylene diene monomer grafted maleic anhydride.
  • 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.
  • 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.
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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 is provided.
  • 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%.
  • BIPB bis-(tert-butylperoxyisopropyl)benzene
  • 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%.
  • DCP dicumyl peroxide
  • 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.
  • the finished product of the ethylene propylene diene monomer grafted maleic anhydride has a yellowish color and the odor of the material is increased.
  • 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.
  • 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%.
  • 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.
  • an analytical grade of hexamethylene phosphate triamine such as that produced by Shanghai Minglong Chemical Co., Ltd. can be used.
  • 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
  • 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[ ⁇ -(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.
  • 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.
  • other antioxidants in the art can also be used.
  • auxiliaries mentioned above include lubricants and/or processing aids.
  • 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:
  • preparing a first solution dissolving the initiator in the component weighed in step S01 in the styrene monomer in the component;
  • 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;
  • 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.
  • 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.
  • the components 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.
  • the mixture is melt extruded and extruded through a twin-screw extruder.
  • 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.
  • 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 °.
  • 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.
  • 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.
  • 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)
  • maleic anhydride uses industrial grade colorless needle crystal structure.
  • antioxidant is four [ ⁇ - (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).
  • 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.
  • 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.
  • 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.
  • 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.
  • the preparation method is as follows:
  • 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.
  • the preparation method is as follows:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ ⁇ lOmin, pressure 15 MPa.
  • Comparative example 5 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 ⁇ ⁇ 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.
  • 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.
  • 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.
  • 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.
  • Example 2 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.
  • Example 3 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%.
  • 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.
  • Example 4 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.
  • Example 5 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.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention porte sur un polymère d'éthylène-propylène-diène greffé anhydride maléique et sur un procédé de préparation correspondant, le polymère d'éthylène-propylène-diène greffé anhydride maléique comprenant les composants de formulation suivants, en pourcentages en poids : 95 %-97 % de polymère d'éthylène-propylène-diène, 0,1 %-0,2 % d'un initiateur, 1 %-2 % d'anhydride maléique, 0,8 %-1,5 % d'un monomère styrène et 0,2 %-0,5 % de triamide hexaméthylphosphorique. La présente invention utilise le polymère d'éthylène-propylène-diène comme substrat de greffage et l'anhydride maléique comme monomère de greffage et effectue le greffage sous l'effet de l'initiateur pendant l'extrusion à l'état fondu. Le taux de greffage et le rendement de greffage sont élevés et le produit a peu d'odeur, une couleur blanche et il est respectueux de l'environnement et sans danger. Le procédé de préparation correspondant a un processus simple, des conditions facilement réglables et il convient à une production industrielle.
PCT/CN2013/074291 2012-04-19 2013-04-17 Polymère d'éthylène-propylène-diène greffé anhydride maléique et procédé de préparation correspondant WO2013155961A1 (fr)

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WO2018115703A1 (fr) * 2016-12-19 2018-06-28 Compagnie Generale Des Etablissements Michelin Procede de preparation d'un elastomere dienique modifie par un compose 1,3-dipolaire par extrusion reactive

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CN102643391B (zh) * 2012-04-19 2014-06-04 深圳市科聚新材料有限公司 一种三元乙丙橡胶接枝马来酸酐及其制备方法
CN106633383A (zh) * 2016-10-21 2017-05-10 安徽江淮汽车集团股份有限公司 一种高性能高透明pp‑ps复合材料及其制备方法
CN108976348B (zh) * 2018-07-05 2020-10-09 上海理工大学 一种旋转蒸发法辅助制备高接枝率的马来酸酐接枝三元乙丙橡胶的方法

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CN101100497A (zh) * 2007-06-08 2008-01-09 深圳市科聚新材料有限公司 通用型双螺杆挤出机一次性挤出的接枝物及其制备方法
CN101302274A (zh) * 2008-05-30 2008-11-12 平顶山华邦工程塑料有限公司 尼龙塑料增韧剂的配比及其生产工艺
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CN102391431A (zh) * 2011-09-01 2012-03-28 浙江俊尔新材料有限公司 一种尼龙增韧剂及其制备方法和应用
CN102643391A (zh) * 2012-04-19 2012-08-22 深圳市科聚新材料有限公司 一种三元乙丙橡胶接枝马来酸酐及其制备方法

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