CN108192027B - Polar polypropylene graft and preparation method thereof - Google Patents
Polar polypropylene graft and preparation method thereof Download PDFInfo
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- CN108192027B CN108192027B CN201711395770.0A CN201711395770A CN108192027B CN 108192027 B CN108192027 B CN 108192027B CN 201711395770 A CN201711395770 A CN 201711395770A CN 108192027 B CN108192027 B CN 108192027B
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
The invention discloses a polar polypropylene graft, which comprises the following components in parts by weight: 100 parts of PP resin raw material; 0.1-5 parts of initiator monomer; 0-2 parts of an initiator; 0-5 parts of polar monomer; 0-5 parts of a grafting auxiliary agent; 0.05-1 part of antioxidant. The invention also discloses a preparation method of the polar polypropylene graft. The polar polypropylene graft is prepared by introducing an initiator monomer simultaneously having a peroxy group, an unsaturated double bond and a polar group and performing a melt reaction extrusion method. The obtained polypropylene graft has higher polar group grafting rate, can effectively reduce common degradation side reaction in the polypropylene melt grafting process, and is beneficial to improving the mechanical property of products. The method is suitable for the existing production process flow and can be used for batch production.
Description
Technical Field
The invention relates to a polypropylene graft, in particular to a polar polypropylene graft and a preparation method thereof.
Background
Polypropylene (PP) is an important general plastic, has excellent physical properties, and is widely applied to various aspects of production and life such as buildings, energy sources, chemical industry, transportation and the like. However, the low surface energy of PP makes most adhesives, inks, coatings, etc. difficult to attach to the surface, and its non-polar chemical nature also makes it difficult to mix with common polar fillers (such as glass fibers, minerals, etc.) uniformly to further improve strength.
The PP structure has a large amount of tertiary carbon and hydrogen atoms, and the tertiary carbon and hydrogen atoms are removed to form macromolecular free radicals under the action of a peroxide initiator, but the free radicals are unstable and are easy to generate β -breakage to cause molecular chain breakage, so that the PP is often accompanied with serious degradation side reaction during graft modification, and the mechanical strength of a product is finally reduced.
In the prior art documents, some technical routes or methods for polar modification of PP while reducing its degradation are disclosed. For example, patent CN101724128A, CN101885806A propose that PP and antioxidant are blended in advance before melt grafting reaction, and then enter an extruder for reaction grafting. The antioxidant has good effects of capturing and quenching free radicals, so that the method can reduce molecular chain breakage of PP, but also prevent the grafting reaction from proceeding, and the grafting rate is reduced. CN103772612A, CN102321217A, CN1456430A, CN101357968A, CN101942061A and other patents disclose a technical route of adding one or more auxiliary grafting monomers during PP grafting, wherein the introduced auxiliary monomers include compounds containing mono-double bond or multiple double bond such as styrene, oleic acid, acrylate and the like. Although the method can reduce side reactions while maintaining the grafting ratio, the introduced auxiliary monomer often has serious pungent odor (such as styrene, acrylic acid and the like), and cannot meet the operation and environmental protection requirements in actual production. In patent CN104804143A, it is proposed to add a small amount of initiator in portions, and to control the concentration of free radicals to maintain smooth reaction to reduce side reactions, which is disadvantageous in that the operation is troublesome, the batch production is difficult, and the use of styrene cannot be completely avoided. Therefore, finding a simple, safe and environment-friendly alternative method to produce high-grafting-rate and low-degradation polar PP grafts has become an important research topic in the industry.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, a first object of the present invention is to provide a polar polypropylene graft having high grafting yield and low degradation.
The second objective of the present invention is to provide a method for preparing polar polypropylene grafts, which can avoid the introduction of high-irritation auxiliary monomers, overcome the degradation problem and the low grafting rate problem in the process of PP grafting reaction, adapt to the existing industrial production process, and realize continuous production.
One of the purposes of the invention is realized by adopting the following technical scheme:
the polar polypropylene graft is characterized by comprising the following components in parts by weight: 100 parts of PP resin raw material; 0.1-5 parts of initiator monomer; 0-2 parts of an initiator; 0-5 parts of polar monomer; 0-5 parts of a grafting auxiliary agent; 0.05-1 part of antioxidant.
Further, the initiator monomer is a compound containing both a peroxide group and a reactive double bond and having a polar functional group.
Further, the initiator monomer is tert-butyl peroxymaleate.
Further, the addition amount of the initiator is 0.1-2 parts by weight, and the initiator is a peroxide initiator; the initiator is selected from one or more of dicumyl peroxide, di-tert-butyl peroxide, benzoyl dichloride peroxide, tert-butyl peroxylaurate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, bis (tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxyacetate. Among them, one or more of dicumyl peroxide, di-t-butyl peroxide and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane are preferable.
Further, the adding amount of the polar monomer is 0.1-5 parts by weight, and the polar monomer is unsaturated carboxylic acid containing polar functional groups and derivatives thereof; the polar monomer is one or more than two of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, 5-norbornane-2, 3-dianhydride, itaconic anhydride, methyl maleic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate.
Further, the grafting aid is added in an amount of 0.1 to 5 parts by weight, and is selected from one or more of styrene, p-methylstyrene, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, polyether polyol triacrylate, triallylisocyanurate, dipentaerythritol hexaacrylate and ditrimethylolpropane acrylate.
Further, the antioxidant is selected from one or more of dilauryl thiodipropionate, antioxidant 1010, antioxidant 1076, antioxidant 1330, antioxidant 168, antioxidant 618, antioxidant 215 and antioxidant 225.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a method for preparing a polar polypropylene graft, comprising:
mixing: uniformly mixing the PP resin raw material and the initiator monomer according to the formula amount to obtain a mixture;
a melt reaction step: placing the mixture in grafting equipment for a melting reaction, wherein the grafting equipment comprises a mixing area, a grafting area and a termination area, wherein the temperature of the mixing area is controlled to be 130-200 ℃, the temperature of the grafting area is controlled to be 150-230 ℃, and the temperature of the termination area is controlled to be 150-220 ℃; adding the initiator, the polar monomer and the grafting assistant in the formula amount into the mixing zone, adding the antioxidant in the formula amount into the termination zone, and extruding and granulating to obtain the polar polypropylene graft.
Further, in the step of the melt reaction, the grafting equipment is a single-screw extruder, the length-diameter ratio of the single screw is 20:1-40:1, the diameter of the screw is 60-120mm, and the rotating speed of the screw is 150-; or the grafting equipment is a double-screw extruder, the length-diameter ratio of the double screws is 28:1-40:1, the diameter of the screws is 35-75mm, and the rotating speed of the screws is 150-500 rpm.
Further, in the step of the melting reaction, the temperature of the mixing area is controlled to be 150-; the temperature of the grafting zone is controlled at 170-220 ℃; the termination zone temperature was controlled at 170-210 ℃.
The invention has the beneficial effects that:
1. the polar polypropylene graft of the present invention has introduced one new kind of reaction component, initiator monomer. The compound has both peroxide group and unsaturated double bond, and has polar functional group. After high-temperature melting initiation, peroxide groups are decomposed to generate free radicals containing polar functional groups, and then the free radicals are grafted to a PP macromolecular chain to obtain polar macromolecular free radicals. On the other hand, the free radical contains a reactive C ═ C double bond, and the macromolecular free radical forms intramolecular cross-links to resist the internal degradation of the PP molecule. Because the molecule contains the initiation group, the reaction group and the polar group at the same time, the decomposition initiation, the grafting and the crosslinking reaction can basically occur in the same molecule, the reaction efficiency is effectively improved, and the higher grafting rate of the polar group is obtained. In addition, the generated surplus free radicals and reactive functional groups can also react with other polar monomers, so that the polarity of the PP graft polymer is further improved. Therefore, the polar polypropylene graft of the present invention has the advantages of high grafting rate and low degradation degree.
2. The preparation method of the invention can avoid introducing high-irritation auxiliary monomers, overcome the problems of degradation and low grafting rate in the PP grafting reaction process, adapt to the existing industrial production process flow and realize continuous production. The polar polypropylene graft prepared by the preparation method has higher polar group grafting rate, can effectively reduce common degradation side reaction in the polypropylene melt grafting process, and is beneficial to improving the mechanical property of products. The method is suitable for the existing production process flow and can be used for batch production.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
A polar polypropylene graft comprises the following components in parts by weight: 100 parts of PP resin raw material; 0.1-5 parts of initiator monomer; 0-2 parts of an initiator; 0-5 parts of polar monomer; 0-5 parts of a grafting auxiliary agent; 0.05-1 part of antioxidant.
As a further embodiment, the PP resin raw material is not particularly limited, and may be selected from one or more mixtures of homo PP, co PP, block PP, and impact PP; the raw material form can be granules, powder or a mixture of the granules and the powder.
In a further embodiment, the initiator monomer is a compound having both a peroxide group and a reactive double bond and having a polar functional group. Preferably, tert-butyl peroxymaleate is used.
As a further embodiment, the components of the polar PP graft also comprise an initiator, but not necessarily, in order to adjust the flowability and process suitability of the product. Preferably, the initiator is a peroxide initiator, and may be one or more selected from dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide dichloride, tert-butyl peroxylaurate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, bis (tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide, tert-butyl peroxybenzoate, and tert-butyl peroxyacetate. Among them, one or more of dicumyl peroxide, di-t-butyl peroxide and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane are preferable.
As a further embodiment, the components of the polar PP grafts also comprise polar monomers, but not necessarily, in order to save costs and increase the grafting of polar groups. Preferably, the polar monomer is an unsaturated carboxylic acid containing a polar functional group and a derivative thereof, and may be one or more selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, 5-norbornane-2, 3-dicarboxylic anhydride, itaconic anhydride, methyl maleic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate. Among them, one or more of acrylic acid, maleic acid and maleic anhydride are preferable.
As a further embodiment, the components of the polar PP grafts also contain a grafting aid, but not necessarily, in order to increase the grafting yield of polar groups and to adjust the product flowability. Preferably, the grafting aid is one or more selected from the group consisting of styrene, p-methylstyrene, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, polyether polyol triacrylate, triallylisocyanurate, dipentaerythritol hexaacrylate and ditrimethylolpropane acrylate. Among them, one or more of styrene, trimethylolpropane triacrylate and triallyl isocyanurate are preferable.
As a further embodiment, the component of the polar PP graft further comprises an antioxidant in order to terminate the reaction and improve the storage stability of the product. Preferably, the antioxidant is one or more selected from dilauryl thiodipropionate, antioxidant 1010, antioxidant 1076, antioxidant 1330, antioxidant 168, antioxidant 618, antioxidant 215 and antioxidant 225. Among them, one or more of antioxidant 1010, antioxidant 1076, antioxidant 168 and antioxidant 215 are preferable.
A method for preparing a polar polypropylene graft, comprising:
mixing: uniformly mixing the PP resin raw material and the initiator monomer according to the formula amount to obtain a mixture;
a melt reaction step: placing the mixture in grafting equipment for a melting reaction, wherein the grafting equipment comprises a mixing area (a front reaction area), a grafting area (a main reaction area) and a termination area, wherein the temperature of the mixing area is controlled to be 130-200 ℃, the temperature of the grafting area is controlled to be 150-230 ℃, and the temperature of the termination area is controlled to be 150-220 ℃; adding the initiator, the polar monomer and the grafting assistant in the formula amount into the mixing zone, adding the antioxidant in the formula amount into the termination zone, and extruding and granulating to obtain the polar polypropylene graft.
As a further embodiment, in the melt reaction step, the grafting device is a single screw extruder, the single screw length to diameter ratio is from 20:1 to 40:1, preferably from 30:1 to 36: 1; the diameter of the screw is 60-120mm, preferably 90 mm; the screw rotation speed is 150-. Or the grafting equipment is a double-screw extruder, the length-diameter ratio of the double screws is 28:1-40:1, preferably 28:1-36: 1; the diameter of the screw is 35-75mm, preferably 65 mm; the screw rotation speed is 150-. A twin-screw extruder is also preferred as the grafting apparatus.
In a further embodiment, in the step of melting reaction, the temperature of the mixing zone is controlled to be 150-190 ℃; the temperature of the grafting zone is controlled at 170-220 ℃; the termination zone temperature was controlled at 170-210 ℃.
In the following, specific examples of the present invention are described, and raw materials, equipment and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Example 1:
a method for preparing a polar polypropylene graft, comprising:
100 parts of a homopolypropylene resin raw material (melt index: 11g/10min (230 ℃ C., 2.16kg)) and 2.5 parts of butyl peroxymaleate were charged into a mixer, and mixed at a stirring speed of 1000r/min for 5 min. The evenly mixed materials are put into a phi 65 twin-screw extruder, the length-diameter ratio of the screw is 36:1, the temperature of the three reaction zones is 190 ℃, and the rotating speed of the screw is 300 rpm. And (3) adding 0.3 part of antioxidant 215 in a terminating zone of an extruder by metering, and extruding and granulating to obtain the polar PP graft.
Example 2:
a method for preparing a polar polypropylene graft, comprising:
100 parts of a homopolypropylene resin raw material (melt index: 11g/10min (230 ℃ C., 2.16kg)) and 5 parts of butyl peroxymaleate were charged into a mixer, and mixed at a stirring speed of 1000r/min for 5 min. The evenly mixed materials are put into a phi 65 twin-screw extruder, the length-diameter ratio of the screw is 36:1, the temperature of the three reaction zones is 190 ℃, and the rotating speed of the screw is 300 rpm. And (3) adding 0.3 part of antioxidant 215 in a terminating zone of an extruder by metering, and extruding and granulating to obtain the polar PP graft.
Example 3:
a method for preparing a polar polypropylene graft, comprising:
100 parts of a homopolypropylene resin raw material (melt index: 11g/10min (230 ℃ C., 2.16kg)) and 0.2 part of butyl peroxymaleate were charged into a mixer, and mixed at a stirring speed of 1000r/min for 5 min. The evenly mixed materials are put into a phi 65 twin-screw extruder, the length-diameter ratio of the screw is 32:1, the temperatures of a mixing zone, a grafting zone and a termination zone are respectively 150 ℃, 190 ℃ and 180 ℃, and the rotating speed of the screw is 300 rpm. 1.3 parts of maleic anhydride and 0.3 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane are metered in the mixing zone of the extruder. And (3) adding 0.1 part of antioxidant 215 in a terminating zone of an extruder by metering, and extruding and granulating to obtain the polar PP graft.
Example 4:
a method for preparing a polar polypropylene graft, comprising:
100 parts of a copolymerized PP resin raw material (melt index: 3.0g/10min (230 ℃ C., 2.16kg)) and 1 part of butyl peroxymaleate were charged into a mixer, and mixed at a stirring speed of 1000r/min for 5 min. The uniformly mixed materials are put into a phi 65 twin-screw extruder, the length-diameter ratio of the screw is 32:1, the temperatures of a mixing zone, a grafting zone and a termination zone are respectively 160 ℃, 210 ℃ and 200 ℃, and the rotating speed of the screw is 300 rpm. 2.5 parts of maleic acid are metered in the mixing zone of the extruder. And (3) adding 0.1 part of antioxidant 168 and 0.1 part of antioxidant 1010 by a metering scale in a termination zone of an extruder, and extruding and granulating to obtain the polar PP graft.
Example 5:
a method for preparing a polar polypropylene graft, comprising:
100 parts of an impact-resistant PP resin raw material (melt index 1.8g/10min (230 ℃, 2.16kg)) and 5 parts of butyl peroxymaleate were charged into a mixer, stirred at 1000r/min and mixed for 5 min. The evenly mixed materials are put into a phi 65 twin-screw extruder, the length-diameter ratio of the screw is 32:1, the temperatures of a mixing zone, a grafting zone and a termination zone are respectively 150 ℃, 220 ℃ and 190 ℃, and the rotating speed of the screw is 200 rpm. 0.1 part of dicumyl peroxide is metered in the mixing zone of the extruder. And (3) adding 0.2 part of antioxidant 168 and 0.1 part of antioxidant 1010 by metering in a termination zone of an extruder, and extruding and granulating to obtain the polar PP graft.
Example 6:
a method for preparing a polar polypropylene graft, comprising:
100 parts of a homopolypropylene resin raw material (melt index: 11g/10min (230 ℃ C., 2.16kg)) and 2.5 parts of butyl peroxymaleate were charged into a mixer, and mixed at a stirring speed of 1000r/min for 5 min. The evenly mixed materials are put into a phi 65 twin-screw extruder, the length-diameter ratio of the screw is 36:1, the temperature of the three reaction zones is 190 ℃, and the rotating speed of the screw is 300 rpm. 0.5 part of trimethylolpropane triacrylate is metered in the mixing zone of the extruder. And (3) adding 0.5 part of antioxidant 215 in a terminating zone of an extruder by metering, and extruding and granulating to obtain the polar PP graft.
Example 7:
a method for preparing a polar polypropylene graft, comprising:
100 parts of a copolymerized PP resin raw material (melt index 8g/10min (230 ℃, 2.16kg)) and 0.5 part of butyl peroxymaleate were charged into a mixer, and mixed at a stirring speed of 1000r/min for 5 min. The uniformly mixed materials are put into a phi 65 twin-screw extruder, the length-diameter ratio of the screw is 36:1, the temperatures of a mixing zone, a grafting zone and a termination zone are respectively 150 ℃, 210 ℃ and 200 ℃, and the rotating speed of the screw is 200 rpm. 1 part of maleic anhydride, 0.2 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and 0.5 part of styrene are metered in the mixing zone of the extruder. And (3) adding 0.05 part of antioxidant 215 in a terminating zone of an extruder by metering, and extruding and granulating to obtain the polar PP graft.
Comparative example 1:
a method of preparing a polypropylene graft, comprising:
100 parts of homopolymerized PP resin raw material (the melt index is 11g/10min (230 ℃, 2.16kg)) is put into a phi 65 twin-screw extruder, the length-diameter ratio of a screw is 36:1, the temperatures of three reaction zones are 190 ℃, and the rotating speed of the screw is 300 rpm. 2.5 parts of maleic acid are metered in the mixing zone of the extruder; 0.3 part of antioxidant 215 was metered into the extruder at the end zone and pelletized by extrusion to give the PP graft of comparative example.
Comparative example 2:
a method of preparing a polypropylene graft, comprising:
100 parts of an impact-resistant PP resin raw material (melt index 1.8g/10min (230 ℃, 2.16kg)) was fed into a phi 65 twin-screw extruder with a screw length-diameter ratio of 32:1, temperatures of the mixing zone, the grafting zone and the termination zone of 150, 220 and 190 ℃ respectively, and a screw rotation speed of 200 rpm. 0.1 part of dicumyl peroxide is metered in the mixing zone of the extruder. 0.2 part of antioxidant 168 and 0.1 part of antioxidant 1010 were metered into the extruder at the end zone and pelletized by extrusion to give the PP graft of comparative example.
Comparative example 3:
a method of preparing a polypropylene graft, comprising:
100 parts of a homopolymeric PP resin raw material (melt index 11g/10min (230 ℃, 2.16kg)) was fed into a phi 65 twin-screw extruder with a screw length-diameter ratio of 32:1, temperatures of the mixing zone, the grafting zone and the termination zone of 150, 190 and 180 ℃ respectively, and a screw rotation speed of 300 rpm. 1.5 parts of maleic anhydride and 0.3 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane are metered in the mixing zone of the extruder. 0.1 part of antioxidant 215 was metered into the extruder at the end zone and pelletized by extrusion to give the PP graft of comparative example.
Comparative example 4:
a method of preparing a polypropylene graft, comprising:
100 parts of a copolymerized PP resin raw material (melt index 8g/10min (230 ℃, 2.16kg)) was fed into a phi 65 twin-screw extruder with a screw length-diameter ratio of 36:1, temperatures of the mixing zone, the grafting zone and the termination zone of 150, 210 and 200 ℃ respectively, and a screw rotation speed of 200 rpm. 1.5 parts of maleic anhydride, 0.2 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and 0.5 part of styrene are metered in the mixing zone of the extruder. 0.05 part of antioxidant 215 was metered into the extruder at the end zone and pelletized by extrusion to give the PP graft of comparative example.
TABLE 1 comparison of PP graft Properties of examples and comparative examples
In Table 1 above, the melt index change rate is reflected in the degree of degradation of the PP before and after the grafting reaction. The greater the melt index change rate, the more degradation. The calculation method is as follows:
in table 1, the method for measuring the graft ratio was performed by acid-base titration. The higher the grafting yield, the more polar the PP graft is.
As can be seen from Table 1, inventive examples 1-7 have lower melt index change rates, indicating less degradation, than comparative examples 1-4; has higher grafting rate, which indicates stronger polarity.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (5)
1. The polar polypropylene graft is characterized by comprising the following components in parts by weight: 100 parts of PP resin raw material; 0.1-5 parts of initiator monomer; 0-2 parts of an initiator; 0.05-1 part of antioxidant; the initiator is a peroxide initiator; the initiator monomer is tert-butyl peroxymaleate;
a method for preparing a polar polypropylene graft, comprising:
mixing: uniformly mixing the PP resin raw material and the initiator monomer according to the formula amount to obtain a mixture;
a melt reaction step: placing the mixture in grafting equipment for a melting reaction, wherein the grafting equipment comprises a mixing area, a grafting area and a termination area, wherein the temperature of the mixing area is controlled to be 130-200 ℃, the temperature of the grafting area is controlled to be 150-230 ℃, and the temperature of the termination area is controlled to be 150-220 ℃; adding the initiator with the formula amount in the mixing area, adding the antioxidant with the formula amount in the termination area, and extruding and granulating to obtain the polar polypropylene graft.
2. The polar polypropylene graft of claim 1, wherein the initiator is added in an amount of 0.1 to 2 parts by weight; the initiator is selected from one or more of dicumyl peroxide, di-tert-butyl peroxide, benzoyl dichloride peroxide, tert-butyl peroxylaurate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, bis (tert-butylperoxyisopropyl) benzene, tert-butylcumyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxyacetate.
3. The polar polypropylene graft of claim 1, wherein the antioxidant is selected from the group consisting of dilauryl thiodipropionate, antioxidant 1010, antioxidant 1076, antioxidant 1330, antioxidant 168, antioxidant 618, antioxidant 215, and antioxidant 225.
4. The polar polypropylene graft of claim 1, wherein in the step of melt reaction, the grafting apparatus is a single screw extruder, the single screw length-diameter ratio is 20:1-40:1, the screw diameter is 60-120mm, and the screw rotation speed is 150-500 rpm; or the grafting equipment is a double-screw extruder, the length-diameter ratio of the double screws is 28:1-40:1, the diameter of the screws is 35-75mm, and the rotating speed of the screws is 150-500 rpm.
5. The polar polypropylene graft of claim 1, wherein in the step of melt reacting, the temperature of the mixing zone is controlled at 150-190 ℃; the temperature of the grafting zone is controlled at 170-220 ℃; the termination zone temperature was controlled at 170-210 ℃.
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| CN111978472A (en) * | 2020-08-27 | 2020-11-24 | 哈尔滨理工大学 | Preparation method of silane grafted modified polypropylene by melting method |
| CN114292363B (en) * | 2021-12-16 | 2023-11-24 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN114380951B (en) * | 2021-12-28 | 2023-09-26 | 金发科技股份有限公司 | Polar component grafted polypropylene material and preparation method and application thereof |
| CN115838454A (en) * | 2023-01-03 | 2023-03-24 | 中化泉州石化有限公司 | Polypropylene graft with low volatile component and high grafting rate and preparation method thereof |
| CN117209670B (en) * | 2023-10-19 | 2024-07-02 | 上海泽明塑胶有限公司 | Grafted polypropylene and preparation method thereof |
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| US4136136A (en) * | 1976-06-14 | 1979-01-23 | The University Of Akron | Graft copolymers of hydrocarbons and small ring heterocyclic compounds and process for the preparation thereof |
| JPWO2007061030A1 (en) * | 2005-11-25 | 2009-05-07 | 三井化学株式会社 | Solar cell sealing material, solar cell sealing sheet, and solar cell module using them |
| CN106905491B (en) * | 2017-01-26 | 2019-10-15 | 厦门内加湖新材料科技有限公司 | Polypropylene-base acid modified grafts and adhesive containing the graft |
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