WO2019206288A1 - 极性单体接枝聚丙烯树脂及其制备方法和应用 - Google Patents

极性单体接枝聚丙烯树脂及其制备方法和应用 Download PDF

Info

Publication number
WO2019206288A1
WO2019206288A1 PCT/CN2019/084622 CN2019084622W WO2019206288A1 WO 2019206288 A1 WO2019206288 A1 WO 2019206288A1 CN 2019084622 W CN2019084622 W CN 2019084622W WO 2019206288 A1 WO2019206288 A1 WO 2019206288A1
Authority
WO
WIPO (PCT)
Prior art keywords
polypropylene resin
hydroxide
polypropylene
polar monomer
grafted polypropylene
Prior art date
Application number
PCT/CN2019/084622
Other languages
English (en)
French (fr)
Inventor
乔金樑
王崧合
张晓红
戚桂村
宋志海
蔡传伦
王湘
赖金梅
李秉海
蒋海斌
茹越
张江茹
高建明
张红彬
韩朋
刘文璐
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201810389343.XA external-priority patent/CN110407981A/zh
Priority claimed from CN201810389316.2A external-priority patent/CN110407962A/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院 filed Critical 中国石油化工股份有限公司
Priority to CA3098221A priority Critical patent/CA3098221A1/en
Priority to JP2020560280A priority patent/JP7447015B2/ja
Priority to US17/051,069 priority patent/US11926687B2/en
Priority to SG11202010438RA priority patent/SG11202010438RA/en
Priority to BR112020021939-8A priority patent/BR112020021939A2/pt
Priority to EP19792130.7A priority patent/EP3786202B1/en
Priority to CN201980026153.4A priority patent/CN112055721A/zh
Publication of WO2019206288A1 publication Critical patent/WO2019206288A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/126—Microwaves
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel

Definitions

  • the invention relates to the technical field of graft modification of polypropylene, in particular to a polar monomer grafted polypropylene resin, a preparation method and application thereof, and a pellet and a product prepared from the grafted polypropylene resin. , composite materials, coatable film materials and bonding materials.
  • Polypropylene is a versatile polymer material with excellent physical and mechanical properties.
  • a common method is to graft a polar monomer such as maleic anhydride onto the polypropylene backbone to increase its polarity.
  • the methods of graft modification mainly include solvent method, melting method and solid phase method.
  • the grafting method achieves a higher grafting rate and a relatively lower reaction temperature.
  • the organic solvent is usually toluene or xylene, so the post-treatment is complicated, the cost is high, and the environmental friendliness is poor, and it has gradually been eliminated in industrial practice.
  • the melt grafting method is currently the most reasonable method and is suitable for industrial production.
  • Chinese patent application CN104804143A reports the use of a twin-screw extruder having a length to diameter ratio of more than 48:1, and a mixed solution of styrene and an initiator is added at various positions of different barrel sections of the extruder to obtain grafting.
  • Maleic anhydride grafted polypropylene having a high rate and no significant decrease in molecular weight compared to the raw material polypropylene.
  • 6,228,948 B1 discloses the use of different process parameters and conditions in various stages of a twin-screw extruder, adding polypropylene and maleic anhydride to an extruder, adding an initiator after melting, and reacting maleic anhydride.
  • the polypropylene is obtained by grafting onto a polypropylene molecular chain to obtain a graft ratio of 2% or more and excellent overall performance.
  • auxiliary monomers can increase the grafting ratio of polypropylene and inhibit the degradation of polypropylene, while using a new initiator to reduce the pungent odor of maleic anhydride grafted polypropylene, the initiator can also be improved
  • the degree of grafting reaction and the degree of copolymerization with the auxiliary monomer are obtained to obtain a maleic anhydride grafted polypropylene having a high graft ratio and a low pungent odor.
  • the ⁇ -broken chain reaction in the melt grafting process of polypropylene is an unavoidable side reaction in the grafting process, so the melt index of the maleic anhydride grafted polypropylene product prepared by the melt grafting method is usually high, that is, The molecular weight is greatly reduced, which causes the mechanical properties of the polypropylene product to deteriorate. Therefore, the main problem faced by the melt grafting method is how to maintain the mechanical properties of the polypropylene matrix while obtaining a sufficiently high graft ratio of maleic anhydride, that is, to maintain the molecular weight substantially unchanged, so that it is not blended with other materials. As for the ultimate mechanical properties of the material.
  • the conventional solid phase method refers to a graft copolymerization reaction in which polypropylene is mixed with a monomer, an initiator, an interface agent, etc., the reaction temperature is low (100 to 140 ° C), and the polypropylene (melting point is about 164 to 171). °C)
  • the polypropylene is still a solid particle at the reaction temperature, so the method is called solid phase grafting.
  • the reaction in the solid phase process is carried out on the exposed polypropylene surface.
  • Chinese patent application CN1283642A discloses a preparation method and application of a solid phase graft copolymer of polypropylene and three monomers, which is a ratio of polypropylene, an initiator and three monomers to a reaction kettle, and a surfactant xylene is added.
  • the solid phase grafting reaction was carried out under a nitrogen atmosphere.
  • Chinese patent application CN103102455A discloses a method for grafting polypropylene, which comprises adding polypropylene, an organic acid (or salt) and a surfactant to a stirred reactor, and after adding the initiator to the reaction temperature, solid phase grafting is carried out.
  • the initiator is a wax-coated peroxide microcapsule.
  • Chinese patent application CN1704436A discloses a continuous solid phase graft production method and apparatus for polypropylene.
  • a production process for solid phase graft modification of polypropylene on a fluidized bed is disclosed in U.S. Patent No. 5,585,435. Both of these techniques achieve high grafting rates by increasing the contact efficiency of the reactants and initiators.
  • the grafted polypropylene resin product should have no initiator residue, and the molecular weight after grafting is not significantly reduced, and the occurrence of ⁇ -broken reaction should be greatly reduced during the preparation process.
  • Another object of the present invention is to provide a polar monomer grafted polypropylene resin which achieves a higher graft ratio.
  • Another object of the present invention is to provide an odorless polar monomer grafted polypropylene resin which is free of residual unreacted monomers or auxiliary grafting monomers.
  • Another object of the present invention is to provide a method for preparing a polar grafted polypropylene resin which is simple in process, easy to handle, simple in production equipment, low in cost, and easy to industrialize.
  • a polar monomer and a solid polypropylene resin which are capable of absorbing microwaves to raise the temperature in the microwave field to above 200 ° C are The above object is achieved by carrying out a graft reaction under microwave irradiation without adding an initiator.
  • the present invention provides a polar monomer grafted polypropylene resin, wherein the grafted polypropylene resin contains no initiator residue, and the polar monomer is capable of absorbing microwaves so that Its temperature in the microwave field rises above 200 °C.
  • microwave refers to electromagnetic waves having a frequency of 300 MHz to 300 GHz.
  • polar monomer refers to a monomer containing a hetero atom such as oxygen, sulfur, nitrogen, halogen or the like or a substituent thereof.
  • the polar monomer that can be used in the present invention is capable of absorbing microwaves to raise the temperature in the microwave field to above 200 °C.
  • the polar monomers that can be used can be determined by the following test methods:
  • the polar monomer was charged into a 10 ml glass vial until the volume of the polar monomer was 2/3 of the volume of the glass vial. Then, a thermocouple is inserted into the glass vial containing the polar monomer, the glass vial is placed in the microwave oven together with the thermocouple, and the microwave is turned on to test the temperature of the polar monomer under microwave irradiation.
  • Any polar monomer having a power of more than 200 ° C in a timely manner can be used as the polar monomer of the present invention.
  • a polar monomer which has been tested to a temperature of more than 200 ° C under the conditions of irradiation with microwave of 700 W power for 30 min can be used in the present invention.
  • the polar monomer may be selected from those polar monomers containing carbon-carbon double bonds, for example, containing a hetero atom selected from oxygen, sulfur, nitrogen, and a halogen, and combinations thereof, or a substituent thereof, and containing a carbon-carbon double bond.
  • Polar monomer may be selected from those polar monomers containing carbon-carbon double bonds, for example, containing a hetero atom selected from oxygen, sulfur, nitrogen, and a halogen, and combinations thereof, or a substituent thereof, and containing a carbon-carbon double bond.
  • the polar monomer may be selected from the group consisting of organic acids, derivatives of organic acids (eg, anhydrides, esters, salts), and combinations thereof, preferably selected from maleic anhydride, maleic anhydride derivatives, (methyl) Acrylic acid, (meth)acrylic acid derivatives (such as glycidyl methacrylate), vinyl acetate, alkenyl sulfonic acid and derivatives thereof, p-styrenecarboxylic acid, p-styrene acetic acid, itaconic acid, oleic acid, peanuts Oleic acids and combinations thereof and their salt forming forms.
  • the (meth)acrylic acid includes acrylic acid, methacrylic acid, and mixtures thereof.
  • the polar monomer is preferably selected from the group consisting of maleic anhydride, maleic anhydride derivatives, (meth)acrylic acid, (meth)acrylic acid derivatives (such as glycidyl methacrylate), vinyl acetate or Several, preferably maleic anhydride, maleic anhydride derivatives, (meth)acrylic acid, (meth)acrylic acid derivatives, more preferably maleic anhydride, and their salt-forming forms.
  • the term "initiator” refers to materials commonly used in the art to initiate polymerization of monomers, including grafting reactions, such as free radical initiators, including peroxide initiators and azo initiators, and redox. Initiator, etc.
  • the peroxide initiator can be further classified into an organic peroxide initiator (for example, dicumyl peroxide) and an inorganic peroxide initiator.
  • the graft ratio may be from 0.01% to 8%, preferably from 0.01% to 6%.
  • the pendant group of the polar monomer exists in the main chain of the polypropylene molecule, for example, the side group of the organic acid or a salt thereof, and the graft ratio of the side group of the organic acid may be 0.01%-8%, preferably 0.01%-6%, more It is preferably from 0.01% to 3%, most preferably from 0.01% to 1.2%.
  • an organic acid salt side group exists on the main chain of the polypropylene molecule, and the graft ratio of the organic acid side group of the side group of the organic acid salt may be 0.01% to 8%, preferably From 0.01% to 6%, more preferably from 0.01% to 3%, most preferably from 0.01% to 1.2%.
  • the organic acid salt side group may include a salt-forming maleic anhydride side group, a maleic anhydride derivative pendant group, a (meth)acrylic acid pendant group, and a (meth)acrylic acid derivative side group (for example, methacrylic acid shrinkage) At least one of a pendant glyceride group and a pendant vinyl acetate group.
  • the graft ratio of the polar monomer is characterized by infrared spectroscopy.
  • the grafted polypropylene resin according to the present invention may have a water contact angle value of less than 90, preferably less than 65, as measured for a film prepared by the solution method from the grafted polypropylene resin.
  • the water contact angle of the side containing the organic acid group in the film after the film formation by the solution method is less than 90, preferably less than 65.
  • the water contact angle value of the surface containing the organic acid salt group in the film is less than 90, preferably 50° to 0°, more preferably 0°.
  • the water contact angle is determined by subjecting the grafted polypropylene resin to a film formation by a solution method, and measuring the water contact angle of the side of the polar monomer-containing side of the obtained film with a water contact angle measuring instrument.
  • the graft index of the grafted polypropylene resin according to the present invention is preferably less than or equal to the melt index of the polypropylene resin as a graft base, that is, its melt index is less than or equal to the raw material of the polypropylene resin before grafting. Melt index.
  • the ⁇ -broken chain reaction of the polypropylene is controlled, and the molecular weight of the polypropylene is not lowered, and the melt index of the grafted polypropylene can be maintained with the raw material polypropylene. Consistent, even lower.
  • melt index is determined in accordance with the standard GB/T3682-2000.
  • polypropylene or "polypropylene resin” as used herein includes homopolymers and copolymers of propylene and mixtures thereof.
  • the polypropylene resin as the graft base may be selected from the group consisting of a propylene homopolymer and a propylene copolymer and a mixture thereof, preferably a random copolymer of propylene.
  • the comonomer in the random copolymer of propylene may be selected from the group consisting of ethylene, an alpha-olefin other than propylene, and combinations thereof, preferably ethylene, C 4 , C 5 , C 6 to C 8 - ⁇ -olefins, and Its combination. More preferably, the random copolymer of propylene contains only ethylene or an ⁇ -olefin other than propylene as a comonomer.
  • the polypropylene resin as the graft base may also be an impact polypropylene resin which contains a rubber phase in addition to the propylene homopolymer.
  • the rubber phase may be a copolymer of propylene and at least one selected from the group consisting of ethylene and an ⁇ -olefin, preferably a comonomer of ethylene, C 4 , C 5 , C 6 to C 8 ⁇ -olefin.
  • the rubber phase of the impact polypropylene resin is formed by polymerizing propylene with ethylene or an ⁇ -olefin other than propylene.
  • the polypropylene resin as the graft base may be in a solid form including a powder, a pellet or an article, and is preferably a polypropylene powder obtained by polymerization using a spherical catalyst.
  • the present invention also provides a process for preparing a polar monomer grafted polypropylene resin according to the present invention, comprising using the polar monomer and a solid polypropylene resin in a microwave irradiation without adding an initiator
  • the step of carrying out the grafting reaction is carried out. It is also possible to use no auxiliary grafting monomer during the grafting reaction.
  • the polar monomer may be used in an amount of from 0.1 to 10% by weight, based on the weight of the solid polypropylene resin as a raw material; preferably from 1 to 8% by weight.
  • the polar monomer can be in the form of a liquid or a solution. If the polar monomer itself is liquid at ambient temperature, the polar monomer itself can be used; in other cases, the polar monomer can be dissolved in a solvent to obtain a solution for use.
  • the solvent may be selected from organic solvents such as at least one of alcohols, ketones, esters, and water, preferably acetone or ethanol.
  • the solid polypropylene resin as a graft base can be used in the form of a powder, pellet or article.
  • the method may include the following steps:
  • the mixture obtained in the step 1) is subjected to microwave irradiation, preferably under an inert gas atmosphere.
  • the polar monomer and the solid polypropylene resin can be thoroughly mixed under vacuum.
  • the solid polypropylene resin can be thoroughly mixed with a polar monomer solution under vacuum.
  • the vacuum facilitates the mixing of the polar monomer with the polypropylene resin, especially for the polypropylene resin with pores, which promotes the grafting monomer into the pores of the polypropylene resin, which is more favorable for the graft reaction.
  • the inert gas in step 2) may be selected from one or more of nitrogen, helium, and argon.
  • step 1) If the polar monomer is in the form of a solution dissolved in a solvent, the mixture obtained in step 1) is dried to remove the solvent prior to step 2).
  • the irradiated mixture obtained in the step 2) is washed to remove unreacted polar monomer and dried.
  • the solvent used for the washing may be selected from organic solvents such as at least one of an alcohol, a ketone, an ester, and water, preferably water.
  • the method of the present invention may comprise the following steps:
  • the irradiated mixture obtained in the step 2) is washed with a solvent to remove the unreacted polar monomer and dried to obtain a polar monomer-grafted polypropylene resin.
  • the solvent in the above step 1') and the step 3) may be selected from at least one of water and an organic solvent, and the two may be the same or different from each other.
  • the above step 1') is used in an amount of the solvent as long as it can dissolve the polar monomer forming solution, and preferably the amount of the obtained polar monomer solution can completely immerse the solid polypropylene resin as a raw material to make it easier for both. Mix well.
  • the weight ratio of polar monomer to solvent may range from (0.1 to 100): 100, preferably from (0.5 to 50): 100, more preferably from (1 to 30):100.
  • the method of the present invention may further comprise the step 4) on the basis of the above steps:
  • the product obtained in the step 3) is subjected to melt extrusion granulation in the case where an additive is optionally added, thereby obtaining pellets of a grafted polypropylene resin.
  • the solid polypropylene resin as a raw material preferably contains no antioxidant.
  • the solid polypropylene resin in the step 1) is preferably a polypropylene resin to which no antioxidant is added, such as a powder.
  • the polypropylene resin raw materials in the prior art all contain a certain antioxidant, and the antioxidant is added at the time of melt extrusion granulation of the polypropylene powder obtained after the polymerization reaction.
  • the solid polypropylene resin or powder of the present invention is preferably a solid polypropylene resin or powder which has not been melt-extruded and granulated by polymerization, and the solid resin or powder at this time is free of an antioxidant.
  • the antioxidant tends to consume free radicals in the subsequent graft modification, so a better grafting effect is achieved using a polypropylene resin without an antioxidant.
  • the solid polypropylene resin used in the method according to the present invention may be various kinds of solid polypropylene resins or powders conventionally used in the prior art, such as homopolypropylene, random copolymer polypropylene, and impact copolymerization. At least one of propylene.
  • the polymerization process of the solid polypropylene resin of the present invention is known in the art.
  • the solid polypropylene resin of the present invention is preferably a polypropylene powder obtained by polymerization using a spherical catalyst.
  • the particles of the polypropylene powder obtained by polymerization of a spherical catalyst are spherical and have many pores on the surface of the particles, so the polypropylene powder is It has a large specific surface area and a large contact area with the polar monomer, which contributes to obtaining a graft product having a higher graft ratio.
  • the comonomer of the random copolymer polypropylene contains at least one of ethylene or an ⁇ -olefin comonomer other than propylene; preferably ethylene, C 4 ⁇ -olefin, C 5 ⁇ -olefin, C 6 ⁇ -olefin to C 8 ⁇ -olefin, more preferably ethylene, 1-butene, 1-heptene, 1-hexene and 1-octene, even more preferably Ethylene and C 4 ⁇ -olefins, still more preferably ethylene and 1-butene, most preferably ethylene.
  • the comonomer may comprise a mixture of the above ethylene and/or an alpha-olefin comonomer other than propylene, preferably only ethylene or an alpha-olefin monomer; in a most preferred embodiment, the random copolymerization Propylene contains only propylene and ethylene.
  • the impact copolymer polypropylene further contains a rubber phase in addition to the propylene homopolymer.
  • the rubber phase is formed by polymerizing propylene with a comonomer which is at least one of ethylene or an ⁇ -olefin other than propylene; preferably ethylene, C 4 ⁇ -olefin, C 5 ⁇ -olefin, C 6 ⁇ -olefin to C 8 ⁇ -olefin, more preferably ethylene, 1-butene, 1-heptene, 1-hexene and 1-octene, still more preferably ethylene and C 4 ⁇ -olefin, still more preferably Ethylene and 1-butene are most preferably ethylene.
  • the rubber phase of the impact copolymerized polypropylene is preferably polymerized from propylene with ethylene or an alpha-olefin other than propylene; in a most preferred embodiment, the rubber phase comprises only a copolymer of propylene and ethylene.
  • the polar monomers that can be used in step 1) are as described above.
  • the step 1) may be carried out by thoroughly mixing the polar monomer and the solid polypropylene resin by various mixing methods known in the art, preferably by a usual stirring method and a stirring apparatus.
  • the stirring device may be a conventional stirring device such as magnetic stirring or mechanical stirring.
  • the drying in the above step 1) may employ various conventional drying methods known in the art including, but not limited to, blast drying, room temperature drying, and the like.
  • the preferred drying temperature is a temperature at which the polypropylene is not melted, for example, not exceeding 160 °C.
  • the irradiation power of the microwave irradiation in the step 2) may be from 100 w to 2000 w, preferably from 500 to 1000 w, more preferably from 600 w to 800 w; and the irradiation time may be from 1 s to 120 min, preferably from 1 min to 30 min, and further preferably from 3 min to 10 min.
  • the microwave irradiation can be carried out in various microwave reactors available in the prior art.
  • the inert gas in the step 2) may include one or more of nitrogen, helium, and argon, preferably nitrogen.
  • the solvent in the step 3) may include at least one of an alcohol, a ketone, an ester, and water, preferably water.
  • the washing of the irradiated mixture in the step 3) is not particularly limited, and the residual polar monomer (for example, an organic acid) can be removed, and a usual washing method can be employed.
  • a usual washing method can be employed.
  • After microwave irradiation immediately use the solvent in a volume exceeding the solid polypropylene resin for a certain period of time (for example, 5-15 minutes), and then use a filtering device to remove excess solvent or moisture; repeat multiple times (such as 2 -6 times) Soaking and filtering to obtain a cleaned solid polypropylene resin.
  • Step 3) Drying as in step 1) various conventional drying methods in the prior art may be employed, including but not limited to, for example, blast drying, room temperature drying, and the like.
  • the preferred drying temperature is a temperature at which the polypropylene is not melted, for example, not exceeding 160 °C.
  • melt extrusion granulation is carried out by using a conventional melt extrusion equipment in plastic processing, and a polar monomer grafted polypropylene resin is subjected to melt extrusion granulation through a conventional melt extrusion equipment to obtain a polar single Granules of bulk grafted polypropylene resin.
  • Useful additives are additives commonly used in the rubber and plastics processing field, such as antioxidants, plasticizers, lubricants, mold release agents (calcium stearate) and the like.
  • the blending temperature of the material is the usual processing temperature of the polypropylene resin, and is selected within a range that ensures that the polypropylene resin is completely melted without decomposing.
  • a common auxiliary agent for polypropylene such as an antioxidant, a plasticizer or the like, may be added to the polar monomer grafted polypropylene resin in a usual amount.
  • a graft product can be obtained by grafting an organic acid or a derivative thereof (for example, an acid anhydride or an ester) with a solid polypropylene resin (for example, a powder) by microwave irradiation. The grafted product is then reacted with a base such as a hydroxide to prepare.
  • a base such as a hydroxide.
  • the organic acid grafted polypropylene powder is thoroughly mixed with an aqueous alkali solution under vacuum to carry out a reaction, optionally using a solvent to remove unreacted alkali and dried, thereby obtaining an organic acid salt grafted polypropylene resin. .
  • the base may be a hydroxide, preferably selected from the group consisting of aqueous ammonia and metal hydroxides such as sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, iron hydroxide, and hydroxide.
  • aqueous ammonia and metal hydroxides such as sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, iron hydroxide, and hydroxide.
  • the preparation method of the organic acid salt grafted polypropylene resin may include the following steps:
  • reaction mixture obtained in the step 4) is washed with a solvent to remove a base which has not been reacted with the organic acid-grafted solid polypropylene resin, and dried to obtain an organic acid salt grafted solid polypropylene resin.
  • the solvent described above is at least one of water and an organic solvent, and at least two of the solvents of the step 1'), the step 3) and the step 5) are the same or different.
  • the hydroxide in the step 1') may be ammonia water or a metal hydroxide, preferably sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, iron hydroxide, hydrogen.
  • a metal hydroxide preferably sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, iron hydroxide, hydrogen.
  • ferrous oxide, zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, barium hydroxide, and rare earth hydroxide more preferably sodium hydroxide, Potassium hydroxide, barium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, most preferably sodium hydroxide, potassium hydroxide or calcium hydroxide.
  • sodium hydroxide preferably sodium hydroxide.
  • the amount of the solvent used for the organic acid or its derivative monomer in the step 1') is as described above for the solvent of the polar monomer.
  • the solvent (preferably water) for dissolving the alkali in the step 1') is also used as long as it can dissolve a base such as a hydroxide to form a solution.
  • a base such as a hydroxide
  • the amount of the resulting alkali solution can be completely impregnated with the organic acid-grafted solid polypropylene resin, which facilitates the thorough mixing and reaction of the two.
  • the weight ratio of the solvent (preferably water) to the base (e.g., hydroxide) may be (0.1-100): 100, preferably (0.5-50): 100, more preferably (1-30): 100.
  • the amount of the base (e.g., hydroxide) may be from 0.1 to 10% by weight, based on the weight of the raw material polypropylene resin used; preferably from 1 to 8% by weight.
  • the drying treatment in the step 1), the step 3) and the step 5) may employ various conventional drying methods in the prior art, including but not limited to, for example, blast drying, room temperature drying, and the like.
  • the preferred drying temperature is a temperature at which the polypropylene is not melted, for example, not exceeding 160 °C.
  • the organic acid grafted solid polypropylene resin and the alkali solution may be sufficiently mixed by various mixing methods in the prior art, preferably by using a usual stirring method and a stirring device.
  • the stirring device may be a conventional stirring device such as magnetic stirring or mechanical stirring.
  • Step 4) The alkali solution is thoroughly mixed with the organic acid grafted solid polypropylene resin and reacted at the same time, and the reaction time is not particularly required until the reaction is sufficient. Generally, after the addition of the alkali solution, the mixture is further mixed and reacted for a certain period of time, for example, it may be 1 to 20 minutes, preferably 2 to 8 minutes.
  • the reaction temperature and pressure are not limited, and are generally normal temperature and pressure.
  • the solvent in step 5) is the same or different from the solvent of step 3) and comprises at least one of an alcohol, a ketone, an ester and water, preferably water.
  • the washing of the reaction mixture after the mixing reaction in the step 5) is not particularly limited, and the residual alkali can be removed, and a usual washing method can be employed. For example, after microwave irradiation, at a high temperature, immediately use a solvent having a volume exceeding that of a solid polypropylene resin (for example, a polypropylene powder) for a certain period of time (for example, 5-15 minutes), and then use a filtering device to remove excess solvent or moisture. The immersion and repeated filtration (for example, 2-6 times) obtains a cleaned solid polypropylene resin.
  • the method preferably further comprises: subjecting the powder obtained in the above step 5) to melt extrusion granulation with optional addition of an additive to obtain pellets of the organic acid salt grafted polypropylene resin.
  • melt extrusion granulation is carried out by using a conventional melt extrusion equipment in plastic processing, and the organic acid salt grafted polypropylene powder is subjected to melt extrusion granulation through a conventional melt extrusion equipment to obtain an organic acid salt joint.
  • Branch polypropylene resin pellets are additives commonly used in the rubber and plastics processing field, such as antioxidants, plasticizers, lubricants, mold release agents (calcium stearate) and the like.
  • the blending temperature of the material is the usual processing temperature of the polypropylene resin, and is selected within a range that ensures that the polypropylene resin is completely melted without decomposing.
  • common additives such as antioxidants, plasticizers and the like can be added to the organic acid salt grafted polypropylene powder in the usual amounts.
  • an inorganic microwave absorbing medium can be used.
  • An inorganic microwave absorbing medium can be added prior to microwave irradiation.
  • the inorganic microwave absorbing medium may be used in an amount of from 0.1 to 10% by weight, based on the weight of the solid polypropylene resin; preferably from 1 to 8% by weight.
  • the inorganic microwave absorbing medium may employ various inorganic materials that can absorb microwaves in the prior art.
  • the inorganic microwave absorbing medium may be selected from metal hydroxides, preferably potassium hydroxide, barium hydroxide, sodium hydroxide, lithium hydroxide, barium hydroxide, calcium hydroxide, iron hydroxide, ferrous hydroxide, Zinc hydroxide, magnesium hydroxide, cobalt hydroxide, gold hydroxide, aluminum hydroxide, copper hydroxide, barium hydroxide, rare earth hydroxide; metal salt, preferably ammonium nitrate, potassium nitrate, sodium nitrate, barium nitrate, nitric acid Calcium, magnesium nitrate, aluminum nitrate, manganese nitrate, zinc nitrate, iron nitrate, ferrous nitrate, copper nitrate, silver nitrate, ammonium chloride, potassium chloride, sodium chloride, barium chloride, calcium chloride, magnesium chloride, chlorine Aluminum,
  • the polar monomer (optionally dissolved in a solvent), the inorganic microwave absorbing medium (optionally dissolved or dispersed in a solvent) may be thoroughly mixed with the solid polypropylene resin prior to microwave irradiation.
  • the polar monomer, the inorganic microwave absorbing medium, and the solid polypropylene resin may be first mixed and then mixed with the other, or may be mixed together.
  • the mixing process is preferably carried out under vacuum conditions.
  • the mixing process can be carried out by various mixing methods commonly used in the prior art, using a common stirring method and a stirring device, such as mechanical stirring mixing, centrifugal mixing, magnetic stirring mixing, etc., so that the polar monomer is sufficiently dissolved in the solvent.
  • the microwave absorbing medium can be sufficiently stably dissolved or dispersed in the solvent, and the mixed materials are thoroughly mixed.
  • the polypropylene resin is first mixed with a polar monomer, optionally dissolved in a solvent, and the resulting mixture is then mixed with an inorganic microwave absorbing medium, optionally dissolved or dispersed in a solvent. .
  • the solvent for dissolving the polar monomer may be the same as or different from the solvent for dissolving or dispersing the inorganic microwave absorbing medium, and is preferably selected from water and an organic solvent (for example, an alcohol, a ketone, an ester).
  • the solvent for dissolving the polar monomer may be selected from at least one of an alcohol, a ketone, an ester, and water, preferably acetone or ethanol.
  • the solvent for dissolving or dispersing the inorganic microwave absorbing medium may be at least one selected from the group consisting of alcohols, ketones, esters, and water, preferably water.
  • the amount of the solvent which dissolves or disperses the microwave absorbing medium can be such that the microwave absorbing medium can be dissolved to form a microwave absorbing medium solution, or the microwave absorbing medium can be sufficiently uniformly dispersed.
  • the amount of the resulting microwave absorbing medium solution or dispersion can be completely immersed in a mixture of the polar monomer and the polypropylene resin, which facilitates thorough mixing and reaction of the three.
  • the weight ratio of the solvent to the microwave absorbing medium in the microwave absorbing medium solution or dispersion may be (0.1-100): 100, preferably (0.5-50): 100, more preferably (1-30): 100.
  • a surfactant conventional in the prior art may be added to the dispersion of the microwave absorbing medium.
  • a surfactant such as a polyoxyethylene type or a polyhydric alcohol type may be used, and the amount is usually from 0.1 to 100% by weight based on the inorganic microwave absorbing medium.
  • the drying treatment may be carried out after the above mixing to remove the solvent in the mixture before microwave irradiation.
  • the microwave absorbing medium can be removed by washing with a solvent after irradiation grafting.
  • the cleaning solvent is at least one selected from the group consisting of water and an organic solvent, preferably at least one selected from the group consisting of alcohols, ketones, esters and water, preferably water.
  • the invention also provides a pellet or article obtained from a grafted polypropylene resin according to the invention, by means of melt extrusion granulation or a further shaping process, optionally with the addition of an additive .
  • additives are additives commonly used in the rubber and plastics processing field, such as antioxidants, plasticizers, lubricants, mold release agents (calcium stearate) and the like.
  • the invention provides a composite material, a coatable film material and a bonding material obtainable by blending the grafted polypropylene resin of the invention with other polymers.
  • the composite material is, for example, an inorganic filler-filled polyolefin composite and a glass fiber reinforced polyolefin composite.
  • the invention also provides the use of the grafted polypropylene resin of the invention for modifying plastics.
  • the polar monomer grafted polypropylene resin of the present invention can be widely used in plastic modification, including but not limited to blending the polar monomer grafted polypropylene resin (pellet or powder) with other polymers.
  • a composite material, a coatable film material, a bonding material, and the like are obtained.
  • the polar monomer grafted polypropylene resin of the present invention can be used as a compatibilizer for blending polypropylene with other polymers in plastic modification; for example, a composite material in which an inorganic material is filled with a polyolefin, In the glass fiber reinforced polyolefin composite material, the film material and the bonding material, the interfacial interaction between the inorganic material or other components and the polypropylene resin is improved, so that the obtained material has excellent comprehensive properties and can be applied to In the fields of automobiles, tools and construction engineering.
  • the invention utilizes the characteristics of microwave selective heating, and performs polar grafting reaction between the polar monomer and the solid polypropylene resin by using microwave irradiation without adding an initiator, thereby preparing an initiator-free residue and the molecular weight is not significantly lowered.
  • Polar monomer grafted polypropylene resin Without being bound by any theory, Applicant believes that solid polypropylene resin (such as powder) is microwave transparent under microwave environment (no or no microwave absorption under microwave irradiation, so it does not generate heat under microwave irradiation), The polar monomer used in the present invention is capable of absorbing microwaves to raise the temperature in the microwave field to above 200 ° C.
  • Such an increase in temperature can cause tertiary carbon in the polypropylene molecular chain near the polar monomer.
  • the atoms are dehydrogenated to generate free radicals, and such radicals further initiate the reaction of the polar monomer to graft onto the polypropylene chain; the elevated temperature is near the melting point of the polypropylene and does not result in polypropylene Broken chain, thus causing grafting reaction but not causing the chain scission reaction of polypropylene; such microwave grafting reaction can greatly avoid the ⁇ -chain scission reaction of polypropylene during melt grafting, without reducing polypropylene
  • the molecular weight keeps the product excellent in mechanical properties.
  • the resulting grafted polypropylene resin does not contain any initiator residues, thereby avoiding the adverse effects of initiator residues on product performance and subsequent processing; in addition, avoiding the addition A large amount of ⁇ -branched reaction of polypropylene caused by the initiator, and the resulting increase in the melt index of the polypropylene and the corresponding decrease in molecular weight, and avoiding the grafting reaction which may occur in the case of adding an initiator Competition with the self-polymerization reaction, thereby increasing the grafting rate.
  • an organic acid grafted polypropylene it is further reacted with a base such as a metal hydroxide to convert the organic acid grafted polypropylene into an organic acid salt grafted polypropylene, which further enhances graft polymerization.
  • a base such as a metal hydroxide
  • the graft ratio of the polar monomer can be increased. Due to the selective heating of the microwave, the inorganic microwave absorbing medium is heated, so that it heats up itself under the microwave environment, thereby promoting the temperature of the polar monomer in the vicinity thereof to rise rapidly to 200 ° C or more, thereby being more effectively induced.
  • the graft reaction does not occur in the chain scission reaction, so that a highly efficient graft reaction can be achieved in a short time and a polar graft polypropylene having a higher graft ratio can be obtained.
  • auxiliary graft monomer is not added in a preferred case and the unreacted polar monomer and the base (for example, hydroxide) can be sufficiently removed, it is possible to obtain a molecular weight which does not significantly decrease, no residual monomer, and no Initiator residue, colorless, odorless, highly polar grafted polypropylene.
  • base for example, hydroxide
  • the preparation method has the advantages of simple preparation process, easy operation, simple production equipment, low cost and easy industrialization.
  • Figure 1 shows an infrared spectrum of a sample of maleic anhydride grafted polypropylene prepared in Examples 1 and 2 according to the present invention.
  • curve a is the curve of pure polypropylene powder
  • curve b is the curve of maleic anhydride grafted polypropylene obtained after microwave irradiation of example 1 for 3 minutes
  • curve c is obtained after microwave irradiation of example 2 for 5 minutes. Curve of maleic anhydride grafted polypropylene.
  • the monomer is grafted in the form of an acid anhydride in the molecular chain of the polypropylene, and after washing with water, a part of the acid anhydride group is opened to form an acid, and part is also an acid anhydride.
  • Fig. 1 the grafted polypropylene samples have an acid anhydride group and a carboxylic acid group, and the extension of the microwave time contributes to the improvement of the graft ratio.
  • FIG. 2 shows infrared spectra of organic acid salt grafted polypropylene samples prepared in Examples S1 and S2 according to the present invention.
  • curve a is the curve of the pure polypropylene powder
  • curve b is the curve of the organic acid salt grafted polypropylene obtained after the microwave irradiation of the embodiment S1 for 3 minutes
  • the curve c is obtained after the microwave irradiation of the embodiment S2 for 5 minutes. Curve of organic acid salt grafted polypropylene.
  • the contact angle measurement sample of the resin was prepared as follows: 4 g of the resin was dissolved in 40 ml of xylene (analytically pure AR), and the resin was sufficiently dissolved in xylene at 120 ° C; then the xylene solution of the resin was poured into a diameter of 100 mm. The film was formed in a watch glass, and the surface dish was placed in an oven at 110 ° C to sufficiently evaporate the solvent to obtain a resin film sample; then the resin film sample was thoroughly washed in ethanol and air-dried to obtain a contact angle measurement sample of the resin.
  • the sample undergoes a phase separation process by a solution process in which the dispersed phase is one side containing a polar monomer (organic acid or organic acid salt) and the other side is only polypropylene.
  • a polar monomer organic acid or organic acid salt
  • One side of the obtained contact angle measurement sample containing the polar monomer side was subjected to water contact angle measurement using the above water contact angle measuring instrument.
  • the sample grafted by the melt method was used.
  • the test procedure was as follows: About 1 g of the grafted polypropylene sample obtained in the comparative example was weighed and placed in 20 ml of xylene, and after completely dissolved by heating, immediately poured into 150 ml of acetone. The unreacted small molecule and the monomer not grafted onto the polypropylene molecule are dissolved in acetone, and the precipitated white floc is a pure graft.
  • the graft ratio of the organic acid salt grafted polypropylene of the present invention can be equivalent to the graft ratio of the organic acid grafted polypropylene obtained by the step of grafting the organic acid to the polypropylene.
  • the microwave reactor used is: SINEO (new instrument) multi-functional microwave synthesis extractor, model: UWave-2000.
  • maleic anhydride (5 parts by mass) was dissolved in acetone (50 parts by mass) to obtain a maleic anhydride acetone solution in terms of 100 parts by mass of the homopolypropylene powder; the maleic anhydride acetone solution was subjected to mechanical stirring under vacuum The mixture was added to the polypropylene powder and thoroughly mixed, and then the mixture was dried (80 ° C blast drying oven). The dried polypropylene/maleic anhydride mixture powder was irradiated with microwave (power 700 W) for 3 min under a nitrogen atmosphere; the microwave irradiated powder was immersed in deionized water for 10 minutes and replaced with deionized water for 3 times.
  • microwave power 700 W
  • the powder was melt-extruded with 0.1 part by mass (based on 100 parts by mass of the homopolypropylene powder), 1010, 0.1 part by mass of the antioxidant 168, and 0.1 part by mass of calcium stearate in a twin-screw extruder.
  • the granulation is carried out, the temperature of the extruder feeding section is 190-200 ° C, the mixing section temperature is 200-210 ° C, the head temperature is 190-200 ° C, and the melt index, contact angle and graft ratio are performed after extrusion granulation. Test, test results are shown in Table 1.
  • maleic anhydride (5 parts by mass) was dissolved in acetone (50 parts by mass) to obtain a maleic anhydride acetone solution in terms of 100 parts by mass of the homopolypropylene powder; sodium chloride (3 parts by mass) was dissolved in deionized An aqueous solution of sodium chloride is obtained in water (50 parts by mass); the maleic anhydride acetone solution is added to the polypropylene powder under vacuum and mechanically mixed, and the mixture is dried (the oven is dried at 80 ° C in a blast drying oven). dry).
  • the dried polypropylene/maleic anhydride mixture powder is thoroughly mixed with the sodium chloride aqueous solution, and then the mixture is dried (80 ° C blast drying oven drying); dried polypropylene/horse after drying
  • the powder of the anhydride/sodium chloride mixture was irradiated by microwave (power: 700 W) for 2 min under a nitrogen atmosphere; the microwave-irradiated powder was immersed in deionized water for 10 minutes and replaced with deionized water for 3 times to ensure removal of un-particulated grafting.
  • the reacted maleic anhydride monomer and sodium chloride were then dried in a blast oven at 80 °C.
  • the powder was melt-extruded with 0.1 part by mass (based on 100 parts by mass of the homopolypropylene powder), 1010, 0.1 part by mass of the antioxidant 168, and 0.1 part by mass of calcium stearate in a twin-screw extruder.
  • the granulation is carried out, the temperature of the extruder feeding section is 190-200 ° C, the mixing section temperature is 200-210 ° C, the head temperature is 190-200 ° C, and the melt index, contact angle and graft ratio are performed after extrusion granulation. Test, test results are shown in Table 1.
  • Example 1 The powder of the polypropylene/maleic anhydride/sodium chloride mixture dried after drying was irradiated for 3 minutes under microwave (power: 700 W) under a nitrogen atmosphere, and the others were the same as in Example 1'.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder is mixed with 0.1 parts by mass of the antioxidant 1010, 0.1 part by mass of the antioxidant 168, and 0.1 parts by mass of calcium stearate is melt-extruded and granulated in a twin-screw extruder, the temperature of the extruder feeding section is 190-200 ° C, the temperature of the mixing section is 200-210 ° C, and the head temperature is 190-200 ° C.
  • the melt index, contact angle and graft ratio were tested after extrusion granulation. The test results are shown in Table 1.
  • the powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated for 5 minutes under microwave (power: 700 W) under a nitrogen atmosphere, and the others were the same as in Example 1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • Example 1 The powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated for 7 minutes under microwave (power: 700 W) under a nitrogen atmosphere, and the others were the same as in Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated for 10 minutes under microwave (power: 700 W) under a nitrogen atmosphere, and the others were the same as in Example 1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated with a microwave (power: 700 W) for 10 minutes under a nitrogen atmosphere, and the others were the same as in Comparative Example 1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • An initiator solution was obtained by dissolving dicumyl peroxide (0.005 parts by mass) in acetone (20 parts by mass) based on 100 parts by mass of the homopolypropylene powder (the same as in Example 1); maleic anhydride (5) The mass of the powder is dry-mixed with the polypropylene powder in a metal cup using a stirring paddle, and the above-mentioned dissolved peroxide initiator solution is added during the mixing.
  • the mixed reactant is melt-extruded and granulated with 0.1 parts by mass of antioxidant 1010, 0.1 part by mass of antioxidant 168 and 0.1 part by mass of calcium stearate in a twin-screw extruder, and the extruder feed section temperature
  • the temperature is 190-200 ° C
  • the mixing section temperature is 200-210 ° C
  • the head temperature is 190-200 ° C
  • the melt index, contact angle and grafting rate are tested after extrusion granulation.
  • the test results are shown in Table 1.
  • a maleic anhydride acetone solution was obtained by dissolving maleic anhydride (1 part by mass) in acetone (50 parts by mass), and the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere (power 700 W). The irradiation was carried out for 7 minutes, and the rest were the same as in Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • a maleic anhydride acetone solution was obtained by dissolving maleic anhydride (1 part by mass) in acetone (50 parts by mass), and the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere (power 700 W). ) Irradiation for 7 min, the rest were the same as Comparative Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • a maleic anhydride acetone solution was obtained by dissolving maleic anhydride (10 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere (power 700 W). The irradiation was carried out for 7 minutes, and the rest were the same as in Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • a maleic anhydride acetone solution was obtained by dissolving maleic anhydride (10 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere (power 700 W). ) Irradiation for 7 min, the rest were the same as Comparative Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the acrylic acid acetone solution was obtained by dissolving acrylic acid (5 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/acrylic acid mixture powder was irradiated for 5 minutes under microwave atmosphere (power: 700 W) under nitrogen atmosphere, and the rest were The same as in the first embodiment.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the acrylic acid acetone solution was obtained by dissolving acrylic acid (5 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/acrylic acid mixture powder was irradiated for 5 minutes under microwave atmosphere (power: 700 W) under nitrogen atmosphere, and the rest were Same as Comparative Example 1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the acrylic acid acetone solution was obtained by dissolving acrylic acid (5 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/acrylic acid mixture powder was irradiated for 7 minutes under microwave atmosphere (power: 700 W) under nitrogen atmosphere. The same as in the first embodiment.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the acrylic acid acetone solution was obtained by dissolving acrylic acid (5 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/acrylic acid mixture powder was irradiated for 7 minutes under microwave atmosphere (power: 700 W) under nitrogen atmosphere. Same as Comparative Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • a methacrylic acid acetone solution was obtained by dissolving methacrylic acid (5 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/methacrylic acid mixture powder was microwaved under a nitrogen atmosphere (power 700 W). The irradiation was carried out for 5 minutes, and the rest were the same as in Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • a methacrylic acid acetone solution was obtained by dissolving methacrylic acid (5 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/methacrylic acid mixture powder was microwaved under a nitrogen atmosphere (power 700 W). ) Irradiation for 5 min, the rest were the same as Comparative Example 1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder of the dried polypropylene/maleic anhydride mixture after drying was irradiated for 5 minutes under microwave atmosphere (power: 700 W) in the same manner as in Example 1 except that 100 parts by mass of the impact copolymer polypropylene powder was used.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder of the polypropylene/maleic anhydride/graphene oxide mixture dried after drying was irradiated with a microwave (power: 700 W) for 2 min under a nitrogen atmosphere, and the others were the same as in Example 11'.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder of the dried polypropylene/maleic anhydride mixture after drying was irradiated for 5 minutes under microwave atmosphere (power: 700 W) in the same manner as in Comparative Example 1, except that 100 parts by mass of the impact copolymer polypropylene powder was used.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder of the dried polypropylene/maleic anhydride mixture after drying was irradiated with a microwave (power: 700 W) for 5 minutes under a nitrogen atmosphere, except that 100 parts by mass of the random copolymer polypropylene powder was used, and the rest were the same as in Example 1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the powder of the dried polypropylene/maleic anhydride mixture after drying was irradiated with a microwave (power: 700 W) for 5 minutes under a nitrogen atmosphere, except for 100 parts by mass of the random copolymer polypropylene powder, and the others were the same as in Comparative Example 1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 1.
  • the graft ratio of the grafted polypropylene under microwave irradiation without the initiator of the present invention is higher than that of the polypropylene blended by melt blending with the initiator.
  • the polypropylene melt index is increased sharply due to the addition of peroxide;
  • the grafting reaction is always higher than that of the sample obtained by adding the peroxide.
  • the higher the graft ratio the lower the water contact angle after film formation.
  • the grafted polypropylene according to the present invention is changed from the non-hydrophilic property (contact angle of more than 90°) of the raw material polypropylene to hydrophilicity.
  • the graft ratio of the grafted polypropylene, the water contact angle, and the melt index can be further improved.
  • the use of the inorganic microwave absorbing medium can achieve a grafted polypropylene resin having similar properties by using a shorter microwave irradiation time than in the case where no inorganic microwave absorbing medium is added, thereby improving production efficiency.
  • Embodiment S1 is a diagrammatic representation of Embodiment S1:
  • maleic anhydride (5 parts by mass) was dissolved in acetone (50 parts by mass) to obtain a maleic anhydride acetone solution in terms of 100 parts by mass of the homopolypropylene powder; sodium hydroxide (5 parts by mass) was dissolved in deionized Aqueous sodium hydroxide solution was obtained in water (50 parts by mass); the maleic anhydride acetone solution was added to the polypropylene powder under vacuum and mechanically mixed, and then the mixture was dried (80 ° C blast drying oven drying) dry).
  • the dried polypropylene/maleic anhydride mixture powder was irradiated by microwave (power 700 W) for 3 min under a nitrogen atmosphere; the microwave irradiated powder was immersed in deionized water for 10 minutes and replaced with deionized water. It is ensured that the maleic anhydride monomer not involved in the grafting reaction is removed, and then the powder is dried in a blast drying oven at 80 ° C; the aqueous sodium hydroxide solution is added to the dried maleic anhydride under vacuum stirring. The grafted polypropylene powder was thoroughly mixed, and after adding an aqueous sodium hydroxide solution, the mixture was stirred and reacted for 5 minutes.
  • the powder is washed by using the deionized water in the same washing step as above and then the powder is dried in a blast drying oven at 80 °C. Finally, the powder was melt-extruded with 0.1 part by mass (based on 100 parts by mass of the homopolypropylene powder), 1010, 0.1 part by mass of the antioxidant 168, and 0.1 part by mass of calcium stearate in a twin-screw extruder.
  • the granulation is carried out, the temperature of the extruder feeding section is 190-200 ° C, the mixing section temperature is 200-210 ° C, the head temperature is 190-200 ° C, and the melt index, contact angle and graft ratio are performed after extrusion granulation. Test, test results are shown in Table 2.
  • Maleic anhydride (5 parts by mass) and dicumyl peroxide (0.005 parts by mass) were dissolved in acetone (50 parts by mass) in 100 parts by mass of the homopolypropylene powder (the same as in Example S1) to obtain a horse.
  • An anhydride acetone solution; sodium hydroxide (5 parts by mass) was dissolved in deionized water (50 parts by mass) to obtain an aqueous sodium hydroxide solution; the maleic anhydride acetone solution was added to the polypropylene powder under vacuum with mechanical stirring. The mixture was thoroughly mixed, and then the mixture was dried (80 ° C blast drying oven).
  • the dried polypropylene/maleic anhydride mixture powder was irradiated by microwave (power 700 W) for 3 min under a nitrogen atmosphere; the microwave irradiated powder was immersed in deionized water for 10 minutes and replaced with deionized water. It is ensured that the maleic anhydride monomer not involved in the grafting reaction is removed, and then the powder is dried in a blast drying oven at 80 ° C; the aqueous sodium hydroxide solution is added to the dried maleic anhydride under vacuum stirring. The grafted polypropylene powder was thoroughly mixed, and after adding an aqueous sodium hydroxide solution, the mixture was stirred and reacted for 5 minutes.
  • the powder is washed by using the deionized water in the same washing step as above and then the powder is dried in a blast drying oven at 80 °C.
  • the powder is melt-extruded and granulated with 0.1 parts by mass of antioxidant 1010, 0.1 parts by mass of antioxidant 168 and 0.1 part by mass of calcium stearate in a twin-screw extruder, and the temperature of the extruder feeding section is 190- 200 ° C, the mixing section temperature is 200-210 ° C, the head temperature is 190-200 ° C, after extrusion granulation, the melt index, contact angle and grafting rate test, the test results are shown in Table 2.
  • Embodiment S2 is a diagrammatic representation of Embodiment S2:
  • Example S1 The powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated for 5 min under microwave (power: 700 W) under a nitrogen atmosphere, and the others were the same as in Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • the powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated for 5 min in a microwave (power: 700 W) under a nitrogen atmosphere, and the others were the same as in Comparative Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S3 is a diagrammatic representation of Embodiment S3:
  • Example S1 The powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated for 7 min in a microwave (power: 700 W) under a nitrogen atmosphere, and the rest were the same as in Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • the powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated for 7 min in a microwave (power: 700 W) under a nitrogen atmosphere, and the others were the same as in Comparative Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S4 is a diagrammatic representation of Embodiment S4:
  • Example S1 The powder of the polypropylene maleic anhydride mixture dried after drying was irradiated by microwave (power: 700 W) for 10 min under a nitrogen atmosphere, and the others were the same as in Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • the powder of the polypropylene/maleic anhydride mixture dried after drying was irradiated by microwave (power: 700 W) for 10 min under a nitrogen atmosphere, and the others were the same as in Comparative Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S5 is a diagrammatic representation of Embodiment S5:
  • Example S1 In addition to dissolving sodium hydroxide (1 part by mass) in deionized water (50 parts by mass) to obtain an aqueous sodium hydroxide solution, the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 5 min, and the rest were the same as in Example S1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 5 min, and the rest were the same as the comparative S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S6 is a diagrammatic representation of Embodiment S6:
  • Example S1 In addition to dissolving sodium hydroxide (8 parts by mass) in deionized water (50 parts by mass) to obtain an aqueous sodium hydroxide solution, the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 5 min, and the rest were the same as in Example S1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Example S1 In addition to dissolving sodium hydroxide (10 parts by mass) in deionized water (50 parts by mass) to obtain an aqueous sodium hydroxide solution, the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 5 min, and the rest were the same as in Example S1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 5 min, and the rest were the same as the comparative S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S8 is a diagrammatic representation of Embodiment S8.
  • Example S1 In addition to dissolving potassium hydroxide (5 parts by mass) in deionized water (50 parts by mass) to obtain an aqueous potassium hydroxide solution, the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 5 min, and the rest were the same as in Example S1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S9 is a diagrammatic representation of Embodiment S9
  • Example S1 In addition to dissolving calcium hydroxide (5 parts by mass) in deionized water (50 parts by mass) to obtain an aqueous calcium hydroxide solution, the powder of the dried polypropylene/maleic anhydride mixture after drying was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 5 min, and the rest were the same as in Example S1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S10 is a diagrammatic representation of Embodiment S10:
  • a maleic anhydride acetone solution was obtained by dissolving maleic anhydride (1 part by mass) in acetone (50 parts by mass), and the powder of the dried polypropylene/maleic anhydride mixture after drying was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 7 min, and the rest were the same as in Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S11 is a diagrammatic representation of Embodiment S11.
  • a maleic anhydride acetone solution was obtained by dissolving maleic anhydride (8 parts by mass) in acetone (50 parts by mass), and the dried polypropylene/maleic anhydride mixture powder was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 7 min, and the rest were the same as in Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S12 is a diagrammatic representation of Embodiment S12:
  • a maleic anhydride acetone solution was obtained by dissolving maleic anhydride (10 parts by mass) in acetone (50 parts by mass), and the powder of the dried polypropylene/maleic anhydride mixture after drying was microwaved under a nitrogen atmosphere ( The power was 700 W) irradiated for 7 min, and the rest were the same as in Example S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S13 is a diagrammatic representation of Embodiment S13.
  • the powder of the dried polypropylene/maleic anhydride mixture after drying was irradiated for 5 min in a microwave (power 700 W) under a nitrogen atmosphere, except for 100 parts by mass of the impact copolymer polypropylene powder, and the rest were in the same manner as in Example S1. the same.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S14 is a diagrammatic representation of Embodiment S14.
  • Embodiment S15 is a diagrammatic representation of Embodiment S15.
  • the powder of the dried polypropylene/maleic anhydride mixture after drying was irradiated for 5 min in a microwave (power 700 W) under a nitrogen atmosphere, except for 100 parts by mass of the random copolymer polypropylene powder, and the rest were in the same manner as in Example S1. the same.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S16 is a diagrammatic representation of Embodiment S16.
  • Embodiment S17 is a diagrammatic representation of Embodiment S17.
  • the acrylic acid acetone solution was obtained by dissolving acrylic acid (5 parts by mass) in acetone (50 parts by mass), and the powder of the dried polypropylene/acrylic acid mixture after drying was irradiated by microwave (power 700 W) for 5 min under a nitrogen atmosphere. The rest are the same as in the embodiment S1.
  • the samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • Embodiment S18 is a diagrammatic representation of Embodiment S18.
  • a methacrylic acid acetone solution was obtained by dissolving methacrylic acid (5 parts by mass) in acetone (50 parts by mass), and the powder of the dried polypropylene methacrylic acid mixture after drying was microwaved under a nitrogen atmosphere (power 700 W). Irradiation for 5 min, the rest were the same as in Example S1. The samples were tested for melt index, contact angle and graft ratio. The test results are shown in Table 2.
  • the examples of the organic acid salt grafted polypropylene under microwave irradiation without the initiator of the present invention are compared with the comparative examples of the polypropylene grafted by melt blending with an initiator.
  • the branching rate is high, and the melt index after the grafting of the polypropylene is not increased, that is, the molecular weight does not decrease.
  • the fracture phenomenon of the main chain of the organic acid salt grafted polypropylene resin obtained in the examples of the present invention is controlled, and the protection is ensured. The mechanical properties of the resin are not lost.
  • the organic acid salt grafted polypropylene according to the embodiment of the present invention is changed from the non-hydrophilic property (contact angle of more than 90°) of the raw material polypropylene to hydrophilicity, and even the contact angle can reach 0°.
  • the water contact angle of the organic acid graft grafted polypropylene having the same graft ratio is significantly smaller than the water contact angle of the organic acid grafted polypropylene, and thus The addition of hydroxide can further increase the polarity of the grafted polypropylene.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本发明涉及聚丙烯接枝改性领域，并提供了极性单体接枝聚丙烯树脂及其制备方法和应用。根据本发明的接枝聚丙烯树脂通过将能够吸收微波从而使其在微波场中的温度升高至高于200℃的极性单体与固体聚丙烯树脂在不添加引发剂的情况下使用微波辐照进行接枝反应而制备。根据本发明获得了不含引发剂残留物并且与接枝前树脂相比分子量不显著下降的极性的接枝聚丙烯树脂。本发明的制备工艺简单，易操作，生产设备简单，成本低，易于工业化。

Description

极性单体接枝聚丙烯树脂及其制备方法和应用 技术领域
本发明涉及聚丙烯接枝改性的技术领域，具体地，涉及一种极性单体接枝的聚丙烯树脂及其制备方法和应用，以及由该接枝聚丙烯树脂制备的粒料、制品、复合材料、可涂覆膜材料和粘接材料。
背景技术
聚丙烯是一种用途很广的通用高分子材料，具有优良的物理力学性能。但是由于聚丙烯的非极性和低表面能，它与大多数聚合物和填料的相容性差，不易润湿、粘合，并且印刷和涂覆性能差，与极性材料共混时也不能获得性能较好的材料。因此，需要一些方法来改善聚丙烯的极性。常见的方法是将马来酸酐等极性单体接枝到聚丙烯主链上来提高其极性。接枝改性的方法主要有溶剂法、熔融法和固相法。
溶剂法实现的接枝率较高，且反应过程温度相对较低。但是，有机溶剂通常为甲苯或二甲苯，因此后处理较复杂，成本高，环境友好性差，已逐渐在工业实践中被淘汰。
熔融接枝法是目前最合理的方法，适合工业化生产。例如，中国专利申请CN104804143A报道了使用长径比大于48：1的双螺杆挤出机，在挤出机的不同螺筒段的多个位置加入苯乙烯和引发剂的混合溶液，获得了接枝率高、与原料聚丙烯相比分子量无明显降低的马来酸酐接枝聚丙烯。美国专利US6,228,948B1报道了在双螺杆挤出机各段采用不同的工艺参数及条件，将聚丙烯、马来酸酐加入挤出机中，待其熔融后加入引发剂，马来酸酐反应接枝到聚丙烯分子链上，得到接枝率2％以上、综合性能优良的聚丙烯。中国专利申请CN102924661A报道了使用辅助单体可以提高聚丙烯接枝率并抑制聚丙烯的降解，同时使用新的引发剂来降低马来酸酐接枝聚丙烯的刺激性气味，该引发剂还能增进接枝反应程度和与辅助单体的共聚程度，获得接枝率高、刺激性气味低的马来酸酐接枝聚丙烯。
但是，聚丙烯熔融接枝过程中的β-断链反应是接枝过程中无法避免的副反应，因此熔融接枝法制备的马来酸酐接枝聚丙烯产品的熔融指数通常都很高，即分子量大幅降低，这会导致聚丙烯产品力学性能变差。因此，熔融接枝法所面临的主要问题是如何在获得足够高马来酸酐接枝率的同时保持聚丙烯基体的力学性能，即保持分子量基本不变，这样在与其他材料共混时才不至于影响材料最终的整体力学性能。传统的固相法是指将聚丙烯与单体、引发剂、界面剂等一起混合后进行的接枝共聚反应，反应温度较低(100～140℃)， 聚丙烯(熔点大约为164～171℃)在反应温度下聚丙烯仍然是固体颗粒，故该方法称为固相接枝法。固相法中反应在暴露的聚丙烯表面进行。中国专利申请CN1283642A公开了一种聚丙烯与三单体固相接枝共聚物的制备方法及应用，是将聚丙烯、引发剂与三种单体按比例投入反应釜，加入界面活性剂二甲苯，在氮气气氛下进行固相接枝反应。中国专利申请CN103102455A公开了一种聚丙烯的接枝方法，将聚丙烯、有机酸(或盐)、界面活性剂加入带搅拌的反应器中，达到反应温度后加入引发剂，进行固相接枝反应，引发剂为蜡包裹过氧化物微胶囊。中国专利申请CN1704436A公开了一种聚丙烯连续固相接枝生产方法和装置。美国专利申请US5,585,435A公开了一种在流化床上进行聚丙烯固相接枝改性的生产方法。这两种技术都是通过提高反应物及引发剂的接触效率而获得高接枝率。
以上所述的现有聚丙烯接枝改性的方法均存在如下缺点：接枝改性导致分子量下降，产品中存在单体残留，改性过程中需使用引发剂，产品有味或者需要特殊设备等。由于极性聚丙烯的应用广泛和市场需求巨大，一种廉价、制备方法简单且不存在上述缺点的接枝聚丙烯成为亟待解决的问题。为解决上述问题，提出本发明。
发明内容
本发明的目的是，提供一种使用微波引发制备的极性单体接枝聚丙烯树脂及其制备方法，其不具有现有接枝聚丙烯树脂和聚丙烯接枝改性方法的不足。所述接枝聚丙烯树脂产品中应无引发剂残留物，接枝后分子量不显著降低，在其制备过程中β-断链反应的发生应大幅降低。
本发明的另一目的是，提供一种极性单体接枝聚丙烯树脂，其可实现较高接枝率。
本发明的另一目的是，提供一种无味的极性单体接枝聚丙烯树脂，其不含残留的未反应单体或辅助接枝单体。
本发明的另一目的是，提供一种极性的接枝聚丙烯树脂的制备方法，其工艺简单，易操作，生产设备简单，成本低，易于工业化。
根据本发明，预料不到地发现，利用微波的选择性加热的性质，通过将能够吸收微波从而使其在微波场中的温度升高至高于200℃的极性单体与固体聚丙烯树脂在不添加引发剂的情况下在微波辐照下进行接枝反应而实现了上述目的。
因此，在第一方面，本发明提供一种极性单体接枝聚丙烯树脂，其中所述接枝聚丙烯树脂内不含引发剂残留物，并且所述极性单体能够吸收微波从而使其在微波场中的温度升高至高于200℃。
本文中使用的术语“微波”是指频率为300MHz-300GHz的电磁波。
本文中使用的术语“极性单体”是指含有氧、硫、氮、卤素等杂原子或其取代基的单体。本发明中可使用的极性单体能够吸收微波从而使其在微波场中的温度升高至高于200℃。
可使用的极性单体可通过如下测试方法确定：
将极性单体装入10ml玻璃药瓶中，直至极性单体的体积占玻璃药瓶体积的2/3。然后，将热电偶插入该装有极性单体的玻璃药瓶中，将该玻璃药瓶连同热电偶一同放入微波炉中，开启微波，测试在微波辐照下极性单体的温度，在任何功率及时长下温度超过200℃的极性单体可用作本发明的极性单体。具体地，例如，在用700W功率的微波辐照30min的条件下，测试到升温至超过200℃的温度的极性单体可用于本发明中。
例如，所述极性单体可以选自含有碳碳双键的那些极性单体，例如含有选自氧、硫、氮和卤素及其组合的杂原子或其取代基并且含有碳碳双键的极性单体。
优选地，所述极性单体可以选自有机酸、有机酸的衍生物(例如酸酐、酯、盐)以及它们的组合，优选选自马来酸酐、马来酸酐衍生物、(甲基)丙烯酸、(甲基)丙烯酸衍生物(例如甲基丙烯酸缩水甘油酯)、乙酸乙烯酯、烯基磺酸及其衍生物、对苯乙烯甲酸、对苯乙烯乙酸、衣康酸、油酸、花生烯酸及其组合以及它们的成盐形式。所述(甲基)丙烯酸包括丙烯酸、甲基丙烯酸及其混合物。
所述极性单体优选选自马来酸酐、马来酸酐衍生物、(甲基)丙烯酸、(甲基)丙烯酸衍生物(例如甲基丙烯酸缩水甘油酯)、乙酸乙烯酯中的一种或几种，优选马来酸酐、马来酸酐衍生物、(甲基)丙烯酸、(甲基)丙烯酸衍生物，更优选马来酸酐，及其成盐形式。
本文中，术语“引发剂”是指本领域常用于引发单体的聚合反应(包括接枝反应)的物质，例如自由基型引发剂，包括过氧化物引发剂和偶氮引发剂及氧化还原引发剂等。过氧化物引发剂又可分为有机过氧化物引发剂(例如过氧化二异丙苯)和无机过氧化物引发剂。
根据本发明的接枝聚丙烯树脂中，接枝率可以为0.01％-8％，优选0.01％-6％。聚丙烯分子主链上存在有极性单体的侧基，例如有机酸或其盐的侧基，有机酸侧基的接枝率可以为0.01％-8％，优选0.01％-6％，更优选0.01％-3％，最优选0.01％-1.2％。对于有机酸盐接枝聚丙烯树脂，聚丙烯分子主链上存在有机酸盐侧基，所述有机酸盐侧基的所述有机酸侧基的接枝率可以为0.01％-8％，优选0.01％-6％，更优选0.01％-3％，最优选0.01％-1.2％。
所述有机酸盐侧基可包括成盐后的马来酸酐侧基、马来酸酐衍生物侧基、(甲基)丙 烯酸侧基、(甲基)丙烯酸衍生物侧基(例如甲基丙烯酸缩水甘油酯侧基)、乙酸乙烯酯侧基中的至少一种。
本文中，极性单体的接枝率通过红外光谱表征。
根据本发明的接枝聚丙烯树脂的水接触角数值可以小于90°，优选小于65°，对于由所述接枝聚丙烯树脂通过溶液法制得的膜测得。例如，对于有机酸接枝聚丙烯树脂，通过溶液法制膜后膜中含有机酸基团一面的水接触角数值小于90°，优选小于65°。对于有机酸盐接枝聚丙烯树脂，通过溶液法制膜后，膜中含有机酸盐基团一面的水接触角数值小于90°，优选为50°-0°，更优选为0°。
本文中，水接触角通过如下方式测定：将接枝聚丙烯树脂经过溶液法制膜，并将所得膜的含极性单体侧基一面用水接触角测定仪器进行水接触角测定。
根据本发明的接枝聚丙烯树脂的熔融指数优选小于或等于作为接枝基础物的所述聚丙烯树脂的熔融指数，也就是说其熔融指数小于或等于所述聚丙烯树脂接枝前原料本身的熔融指数。本发明的极性单体接枝聚丙烯树脂的制备过程中聚丙烯的β-断链反应受到控制，不会发生聚丙烯分子量降低的现象，接枝聚丙烯的熔融指数能够与原料聚丙烯保持一致，甚至降低。
在本文中，熔融指数按照标准GB/T3682-2000进行测定。
本文中所用术语“聚丙烯”或“聚丙烯树脂”包括丙烯的均聚物和共聚物及其混合物。
作为接枝基础物的聚丙烯树脂可选自丙烯均聚物和丙烯共聚物及其混合物，优选丙烯的无规共聚物。例如，所述丙烯的无规共聚物中的共聚单体可以选自乙烯、除了丙烯以外的α-烯烃及其组合，优选乙烯、C 4、C 5、C 6至C 8-α-烯烃及其组合。更优选，所述丙烯的无规共聚物中只包含乙烯或一种除了丙烯以外的α-烯烃作为共聚单体。
作为接枝基础物的聚丙烯树脂也可以是抗冲聚丙烯树脂，其除了包含丙烯均聚物外还包含橡胶相。所述橡胶相可以是由丙烯与选自乙烯、α-烯烃中的至少一种，优选乙烯、C 4、C 5、C 6至C 8α-烯烃的共聚单体形成的共聚物。优选，所述抗冲聚丙烯树脂的橡胶相是由丙烯与乙烯或一种除了丙烯以外的α-烯烃聚合而形成的。
作为接枝基础物的聚丙烯树脂可以是包括粉料、粒料或制品的固体形式，优选的是使用球形催化剂进行聚合得到的聚丙烯粉料。
极性单体接枝聚丙烯树脂的制备方法
在第二方面，本发明还提供根据本发明的极性单体接枝聚丙烯树脂的制备方法，包括 将所述极性单体与固体聚丙烯树脂在不添加引发剂的情况下使用微波辐照进行接枝反应的步骤。在该接枝反应过程中也可以不使用辅助接枝单体。
在本发明方法中，所述极性单体的用量可以为基于作为原料的固体聚丙烯树脂重量计的0.1-10％重量；优选1-8％重量。
所述极性单体可以为液体或溶液形式。如果极性单体自身在环境温度下是液体，则可以使用极性单体自身；在其他情况下，可以将极性单体溶解在溶剂中得到溶液来使用。所述溶剂可以选自有机溶剂，例如醇、酮、酯，和水中的至少一种，优选丙酮或乙醇。
作为接枝基础物的固体聚丙烯树脂可以粉料、粒料或制品形式使用。
具体地，所述方法可以包括以下步骤：
1)将极性单体与固体聚丙烯树脂进行充分混合；
2)对步骤1)中所得混合物进行微波辐照，优选在惰性气体气氛下进行。
在步骤1)中，极性单体与固体聚丙烯树脂可以在真空条件下充分混合。例如，所述的固体聚丙烯树脂可以与极性单体溶液在真空条件下充分混合。真空有利于极性单体与聚丙烯树脂混合得更充分，尤其对于带有孔隙的聚丙烯树脂来说，促进接枝单体进入到聚丙烯树脂孔隙中，更有利于接枝反应。
步骤2)中所述惰性气体可以选自氮气、氦气、氩气中的一种或多种。
如果所述极性单体为溶解在溶剂中的溶液形式，则在步骤2)之前对步骤1)中所得混合物进行干燥以除去溶剂。
如果需要的话，将步骤2)中获得的辐照后的混合物进行清洗以除去未反应的极性单体，并进行干燥。用于清洗的溶剂可以选自有机溶剂，例如醇、酮、酯，水中的至少一种，优选水。
更具体地，本发明的方法可以包括以下步骤：
1’)将极性单体在溶剂中溶解，得到极性单体溶液；
1)将固体聚丙烯树脂与步骤1’)所得的极性单体溶液充分混合，然后进行干燥处理；
2)将步骤1)所得的混合物进行微波辐照，优选在惰性气体气氛下进行；
3)将步骤2)取得的辐照后的混合物使用溶剂清洗，去除未反应的极性单体并干燥处理，得到极性单体接枝的聚丙烯树脂。以上所述步骤1’)和步骤3)中的溶剂均可选自水、有机溶剂中的至少一种，两者可相同或彼此不同。
以上所述步骤1’)溶剂的用量只要能够溶解极性单体形成溶液即可，优选所得的极性单体溶液的量可以使得完全浸没作为原料的固体聚丙烯树脂，以更便于两者的充分混合。 通常极性单体与溶剂的重量比可以在(0.1-100):100，优选(0.5-50):100，更优选(1-30):100范围内。
进一步地，本发明的方法还可以在以上步骤的基础上包括步骤4)：
将步骤3)得到的产物，在任选添加添加剂的情况下，进行熔融挤出造粒，从而得到接枝聚丙烯树脂的粒料。
根据本发明的方法中，作为原料的固体聚丙烯树脂优选不含抗氧剂。步骤1)中所述固体聚丙烯树脂优选为未添加抗氧剂的聚丙烯树脂，例如粉料。通常现有技术中的聚丙烯树脂原料都含有一定的抗氧剂，抗氧剂是在聚合反应后得到的聚丙烯粉料熔融挤出造粒的时候加入的。本发明的固体聚丙烯树脂或粉料优选用聚合得到的还未熔融挤出造粒的固体聚丙烯树脂或粉料，此时的固体树脂或粉料是不含抗氧剂的。抗氧剂容易在后面的接枝改性中消耗自由基，因此使用不加抗氧剂的聚丙烯树脂实现了更好的接枝效果。
根据本发明的方法中使用的所述固体聚丙烯树脂可采用现有技术中通常的各种种类的固体聚丙烯树脂或粉料，例如均聚聚丙烯、无规共聚聚丙烯、抗冲共聚聚丙烯中的至少一种。
本发明的固体聚丙烯树脂的聚合工艺是现有技术中已知的。本发明固体聚丙烯树脂优选为使用球形催化剂聚合得到的聚丙烯粉料，这种通过球形催化剂聚合得到的聚丙烯粉料的颗粒是球形的且颗粒表面具有很多孔隙，因此该种聚丙烯粉料具有很大的比表面积，与极性单体接触的面积大，这有助于获得较高接枝率的接枝产物。
当本发明的聚丙烯树脂为无规共聚聚丙烯时，所述无规共聚聚丙烯的共聚单体包含有乙烯或除丙烯外的α-烯烃共聚单体中的至少一种；优选乙烯、C 4α-烯烃、C 5α-烯烃、C 6α-烯烃至C 8α-烯烃，更优选乙烯、1-丁烯、1-庚烯，1-己烯和1-辛烯，再更优选乙烯和C 4α-烯烃，再更优选乙烯和1-丁烯，最优选为乙烯。所述共聚单体可包含上述乙烯和/或除丙烯外的α-烯烃共聚单体的混合物，优选只为乙烯或一种α-烯烃单体；在最优选的实施方案中，该无规共聚丙烯仅含丙烯和乙烯。
当本发明的固体聚丙烯树脂为抗冲共聚聚丙烯时，所述抗冲共聚聚丙烯除含有丙烯均聚物外还包含橡胶相。橡胶相是由丙烯与共聚单体聚合而成，所述共聚单体为乙烯或除丙烯外的α-烯烃中的至少一种；优选乙烯、C 4α-烯烃、C 5α-烯烃、C 6α-烯烃至C 8α-烯烃，更优选乙烯、1-丁烯、1-庚烯，1-己烯和1-辛烯，再更优选乙烯和C 4α-烯烃，再更优选为乙烯和1-丁烯，最优选为乙烯。所述抗冲共聚聚丙烯的橡胶相优选由丙烯与乙烯或一种除丙烯外的α-烯烃聚合而成；在最优选的实施方案中，该橡胶相仅含丙烯和乙烯的共聚物。
步骤1)中可使用的极性单体如上文已经描述。
步骤1)中可采用现有技术中已知的各种混合方法来对极性单体和固体聚丙烯树脂进行充分混合，优选采用通常的搅拌方式及搅拌设备进行。其中搅拌设备可为磁力搅拌、机械搅拌等常规搅拌装置。
上述步骤1)中的干燥可采用现有技术中已知的各种常规干燥方法，包括但不限于如鼓风干燥、常温干燥等。优选的干燥温度是不使聚丙烯发生熔融的温度，例如不超过160℃。
步骤2)中所述微波辐照的辐照功率可以为100w-2000w，优选为500-1000w，更优选600w-800w；辐射时间可以为1s-120min，优选1min-30min，再优选3min-10min。所述的微波辐照可采用现有技术中已有的各种微波反应器中进行。
步骤2)中所述惰性气体可以包括氮气、氦气、氩气中的一种或多种，优选氮气。
步骤3)中所述溶剂可以包括醇、酮、酯、水中的至少一种，优选水。
步骤3)中对辐照后的混合物的清洗没有特殊限定，能够将残余的极性单体(例如有机酸)去除即可，可采用通常的清洗方法。比如在微波辐照后在高温的情况下立即使用体积超过固体聚丙烯树脂的所述溶剂浸泡一定时间(比如5-15分钟)，然后使用过滤装置去除多余溶剂或水分；重复多次(比如2-6次)浸泡、过滤即得到清洗干净的固体聚丙烯树脂。步骤3)干燥同步骤1)，可采用现有技术中各种常规干燥方法，包括但不限于如鼓风干燥、常温干燥等。优选的干燥温度是不使聚丙烯发生熔融的温度，例如不超过160℃。
步骤4)中熔融挤出造粒是利用塑料加工中通常的熔融挤出设备，将极性单体接枝聚丙烯树脂通过常规的熔融挤出设备，进行熔融挤出造粒制得极性单体接枝聚丙烯树脂的粒料。可用的添加剂是橡塑加工领域通常使用的添加剂，例如抗氧剂、增塑剂、润滑剂、脱模剂(硬脂酸钙)等。
在制备过程中，物料的共混温度是聚丙烯树脂的通常加工温度，在既保证聚丙烯树脂完全熔融又不会使其分解的范围内选择。此外，根据加工需要，可在极性单体接枝聚丙烯树脂中按通常用量加入聚丙烯的常用助剂，比如抗氧剂、增塑剂等。
有机酸盐接枝的聚丙烯树脂的制备方法
为了制备有机酸盐接枝的聚丙烯树脂，可以通过将有机酸或其衍生物(例如酸酐或酯)与固体聚丙烯树脂(例如粉料)使用微波辐照进行接枝反应得到接枝产物，再将接枝产物与碱(例如氢氧化物)反应制备。本文中术语“有机酸接枝聚丙烯”或“有机酸接枝固体聚丙烯树脂”包括有机酸或其酸酐或酯接枝的聚丙烯或固体聚丙烯树脂。
优选，将有机酸接枝聚丙烯粉料与碱的水溶液在真空下充分混合进行反应，任选地使用溶剂清洗去除未反应的碱并进行干燥处理，从而得到有机酸盐接枝的聚丙烯树脂。
所述碱可以是氢氧化物，优选选自氨水和金属氢氧化物，例如氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物，优选选自氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙，及其组合。
具体地，有机酸盐接枝聚丙烯树脂的制备方法可以包括以下步骤：
1’)将有机酸或其衍生物单体在溶剂中溶解，得到有机酸或其衍生物单体溶液；将碱(例如氢氧化物)在溶剂(例如水)中溶解，得到碱的溶液(优选水溶液)；
1)将固体聚丙烯树脂(例如粉料)与步骤1’)所得的有机酸或其衍生物单体溶液充分混合，然后进行干燥处理；
2)将步骤1)所得的混合物进行微波辐照，优选在惰性气体气氛下进行；
3)将步骤2)取得的辐照后的混合物使用溶剂清洗，去除未反应的有机酸或其衍生物单体并干燥处理，得到有机酸接枝固体聚丙烯树脂；
4)将步骤3)得到的有机酸接枝固体聚丙烯树脂与步骤1’)准备的碱溶液在真空下充分混合进行反应；
5)将步骤4)取得的反应混合物使用溶剂清洗，去除未与有机酸接枝固体聚丙烯树脂反应的碱并进行干燥处理，得到有机酸盐接枝固体聚丙烯树脂。
以上所述溶剂为水、有机溶剂中的至少一种，所述步骤1’)、步骤3)和步骤5)的溶剂中至少两者相同或者都不相同。
步骤1’)中所述氢氧化物可以为氨水、金属氢氧化物，优选为氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物中的一种或几种，更优选氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙，最优选氢氧化钠、氢氧化钾、氢氧化钙。最优选氢氧化钠。
步骤1’)中用于有机酸或其衍生物单体的溶剂的用量如上文中对于极性单体的溶剂所述。
步骤1’)中用于溶解碱的溶剂(优选水)的用量也是只要能够溶解碱，例如氢氧化物形成溶液的即可。优选所得的碱溶液的量可以完全浸没有机酸接枝固体聚丙烯树脂，更便于两者的充分混合和反应。通常，所述溶剂(优选水)与碱(例如氢氧化物)的重量比可 以为(0.1-100):100，优选(0.5-50):100，更优选(1-30):100。所述碱(例如氢氧化物)用量可以为基于所用原料聚丙烯树脂重量的0.1-10％重量；优选1-8％重量。
在该方法中，步骤1)、步骤3)及步骤5)中的干燥处理可采用现有技术中各种常规干燥方法，包括但不限于如鼓风干燥、常温干燥等。优选的干燥温度是不使聚丙烯产生熔融的温度，例如不超过160℃。
步骤4)中可采用现有技术中各种混合方法来对有机酸接枝固体聚丙烯树脂与碱溶液进行充分混合，优选采用通常的搅拌方式及搅拌设备进行。其中搅拌设备可为磁力搅拌、机械搅拌等常规搅拌装置。
步骤4)中碱溶液与有机酸接枝固体聚丙烯树脂充分混合并同时反应，其反应时间无特殊要求，至充分反应即可。一般是在碱溶液添加完毕后进一步混合同时反应一段时间即可，比如可以在1-20分钟，优选2-8分钟。其反应温度及压力都无限制，一般为常温常压。
步骤5)中所述溶剂与步骤3)所述溶剂相同或不同，包括醇、酮、酯、水中的至少一种，优选水。步骤5)中对混合反应后的反应混合物的清洗没有特殊限定，能够将残余的碱去除即可，可采用通常的清洗方法。比如在微波辐照后在高温的情况下立即使用体积超过固体聚丙烯树脂(例如聚丙烯粉料)的所述溶剂浸泡一定时间(比如5-15分钟)，然后使用过滤装置去除多余溶剂或水分；重复多次(比如2-6次)浸泡、过滤即得到清洗干净的固体聚丙烯树脂。
该方法优选进一步包括：将以上步骤5)得到的粉料，在任选添加添加剂的情况下进行熔融挤出造粒，得到有机酸盐接枝聚丙烯树脂的粒料。在此，熔融挤出造粒是利用塑料加工中通常的熔融挤出设备，将有机酸盐接枝聚丙烯粉料通过常规的熔融挤出设备，进行熔融挤出造粒制得有机酸盐接枝聚丙烯树脂粒料。可用的添加剂是橡塑加工领域通常使用的添加剂，例如抗氧剂、增塑剂、润滑剂、脱模剂(硬脂酸钙)等。
在制备过程中，物料的共混温度是聚丙烯树脂的通常加工温度，在既保证聚丙烯树脂完全熔融又不会使其分解的范围内选择。此外，根据加工需要，可在有机酸盐接枝聚丙烯粉料中按通常用量加入聚丙烯的常用助剂，比如抗氧剂、增塑剂等。
使用无机微波吸收介质的制备方法
在根据本发明的制备方法的一种实施方案中，可以使用无机微波吸收介质。
可以在微波辐照之前添加无机微波吸收介质。所述无机微波吸收介质的用量可以为基 于固体聚丙烯树脂重量计的0.1-10％重量；优选为1-8％重量。
所述无机微波吸收介质可采用现有技术中的各种可以吸收微波的无机物。例如，所述无机微波吸收介质可以选自金属氢氧化物，优选氢氧化钾、氢氧化钡、氢氧化钠、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物；金属盐，优选硝酸铵、硝酸钾、硝酸钠、硝酸钡、硝酸钙、硝酸镁、硝酸铝、硝酸锰、硝酸锌、硝酸铁、硝酸亚铁、硝酸铜、硝酸银、氯化铵、氯化钾、氯化钠、氯化钡、氯化钙、氯化镁、氯化铝、氯化锰、氯化锌、氯化铁、氯化亚铁、氯化铜、硫酸铵、硫酸钾、硫酸钠、硫酸钙、硫酸镁、硫酸铝、硫酸锰、硫酸锌、硫酸铁、硫酸亚铁、硫酸铜、硫酸银、碳酸铵、碳酸钾、碳酸钠、碳酸镁、碳酸钙、碳酸钡、磷酸二氢钾、钛酸钡、钛酸锶、钛酸铜钙；金属氧化物，优选三氧化二铁、四氧化三铁；石墨类材料，优选炭黑、石墨粉、氧化石墨烯及其还原产物(还原剂例如为抗坏血酸)、石墨烯、碳纳米管、活性炭；铁电类材料；电解石；黄铜矿；以及它们的组合。
可以在微波辐照之前将极性单体(任选地溶解于溶剂中)、无机微波吸收介质(任选地溶解或分散于溶剂中)与固体聚丙烯树脂充分混合。可以首先将极性单体、无机微波吸收介质与固体聚丙烯树脂中的两者混合，然后再与另一者混合，也可以三者一起混合。所述混合过程优选在真空条件下进行。
所述混合过程可采用现有技术中常用的各种混合方法，采用通常的搅拌方式及搅拌设备进行，比如机械搅拌混合、离心混合、磁力搅拌混合等，使得极性单体充分溶解于溶剂中，微波吸收介质能充分稳定地溶解或分散在溶剂中，被混合的物质充分混合。
在一种实施方案中，首先将所述聚丙烯树脂与任选地溶解于溶剂中的极性单体混合，然后将形成的混合物与任选地溶解或分散于溶剂中的无机微波吸收介质混合。
所述用于溶解极性单体的溶剂与用于溶解或分散无机微波吸收介质的溶剂可以相同或不同，优选选自水和有机溶剂(例如醇、酮、酯)。用于溶解极性单体的溶剂可以选自醇、酮、酯、水中至少一种，优选丙酮或乙醇。用于溶解或分散无机微波吸收介质的溶剂可以选自醇、酮、酯、水中至少一种，优选水。
溶解或分散微波吸收介质的溶剂用量只要能够溶解微波吸收介质形成微波吸收介质 溶液、或是能够使得微波吸收介质充分均匀分散即可。优选所得的微波吸收介质溶液或分散体的量可以完全浸没极性单体和聚丙烯树脂的混合物，更便于三者的充分混合和反应。通常微波吸收介质溶液或分散体中溶剂与微波吸收介质的重量比可以为(0.1-100):100，优选(0.5-50):100，更优选(1-30):100。
为了保障微波吸收介质能够与溶剂形成充分分散稳定的分散体，可以在所述微波吸收介质分散体中加入现有技术中通常的表面活性剂。一般可以选用聚氧乙烯型、多元醇型等表面活性剂，用量通常为无机微波吸收介质的0.1-100％重量。
优选地，可以在上述混合后进行干燥处理，以在微波辐照之前去除混合物中的溶剂。微波吸收介质在辐照接枝后可使用溶剂清洗除去。所述清洗用溶剂选自水、有机溶剂中的至少一种，优选自醇、酮、酯、水中至少一种，优选水。
进一步的产品和应用
在本发明的第三方面，本发明还提供粒料或制品，其由根据本发明的接枝聚丙烯树脂，在任选添加添加剂的情况下，通过熔融挤出造粒或进一步的成型工艺获得。可用的添加剂是橡塑加工领域通常使用的添加剂，例如抗氧剂、增塑剂、润滑剂、脱模剂(硬脂酸钙)等。
在本发明的第四方面，本发明提供复合材料、可涂覆膜材料和粘接材料，其可通过将本发明的接枝聚丙烯树脂与其他聚合物共混获得。所述复合材料例如是无机物填充聚烯烃的复合材料和玻纤增强聚烯烃复合材料。
在本发明的第五方面，本发明还提供本发明的接枝聚丙烯树脂用于改性塑料的用途。
本发明的极性单体接枝聚丙烯树脂可广泛应用在塑料改性中，包括但不限于将所述极性单体接枝聚丙烯树脂(粒料或粉料)与其他聚合物共混制得复合材料、可涂覆膜材料和粘接材料等。具体来讲，本发明所述极性单体接枝聚丙烯树脂在塑料改性中可以作为聚丙烯与其他聚合物共混复合时的增容剂；比如在无机物填充聚烯烃的复合材料、玻纤增强聚烯烃复合材料、可涂覆膜材料和粘接材料等材料中，提高无机材料或其他组分与聚丙烯树脂的界面相互作用，使得所得的材料具有优异的综合性能，可应用于汽车、工具和建筑工程等领域。
本发明利用微波选择性加热的特点，将极性单体与固体聚丙烯树脂使用微波辐照在不添加引发剂的情况下进行接枝反应，从而制备得到无引发剂残留物并且分子量不显著降低 的极性单体接枝聚丙烯树脂。不受任何理论的束缚，申请人认为，固体聚丙烯树脂(例如粉料)在微波环境下是微波透明的(微波辐照下很少或者不吸收微波，因此在微波辐照下不发热)，而本发明中使用的极性单体能够吸收微波从而使其在微波场中的温度升高至高于200℃，这样的温度升高能引起在极性单体附近的聚丙烯分子链中的叔碳原子脱氢，从而产生自由基，而这样的自由基进一步引发极性单体的反应，从而接枝到聚丙烯链上；所述升高的温度在聚丙烯熔点附近，不会导致聚丙烯的断链，因此会导致发生接枝反应但不会造成聚丙烯的断链反应；这样的微波接枝反应可以大幅避免熔融法接枝时的聚丙烯的β-断链反应，不降低聚丙烯的分子量，使制品保持优异的力学性能。由于本发明的方法中不添加引发剂，所得接枝聚丙烯树脂不会含有任何引发剂残留物，由此避免了引发剂残留物对产品性能和后续加工的不利影响；另外，避免了在添加引发剂情况下造成的聚丙烯大量的β-断链反应，以及由此导致的聚丙烯熔融指数的升高和相应的分子量的下降，并且避免了在添加引发剂情况下可能发生的接枝反应与自聚反应的竞争，由此提高了接枝率。
在有机酸接枝聚丙烯的情况下，将其进一步与碱(例如金属氢氧化物)反应，可将有机酸接枝聚丙烯转化成有机酸盐接枝聚丙烯，这将进一步提高接枝聚丙烯的极性。
在添加微波吸收介质的优选情况下，可以提高极性单体的接枝率。由于微波的选择性加热，无机微波吸收介质被加热，使得其在微波环境下自身升温，进而可促进在其附近的极性单体的温度快速升高到200℃以上，由此更有效地引发接枝反应但不发生断链反应，从而可以在短时间内实现高效的接枝反应并得到较高接枝率的极性聚丙烯。
另外，由于在优选的情况下也不添加辅助接枝单体并且可以将未反应的极性单体及碱(例如氢氧化物)充分去除，可以获得分子量不显著下降、无残留单体、无引发剂残留物、无色无味的极性高的接枝聚丙烯。
本发明制备工艺简单，易操作，生产设备简单，成本低，易于工业化。
附图说明
图1显示根据本发明的实施例1和2中制备的马来酸酐接枝聚丙烯样品的红外谱图。其中曲线a为纯聚丙烯粉料的曲线，曲线b为实施例1的微波辐照3min后得到的马来酸酐接枝聚丙烯的曲线，曲线c为实施例2的微波辐照5min后得到的马来酸酐接枝聚丙烯的曲线。
对于所述有机酸接枝聚丙烯，单体是以酸酐形式接枝在聚丙烯分子链的，经过水洗，部分酸酐基团开环成为酸，部分还是酸酐。从图1可以看出接枝完毕的聚丙烯样品均具有 酸酐基团和羧酸基团，且微波时间的延长有助于接枝率的提升。
图2显示根据本发明的实施例S1和S2中制备的有机酸盐接枝聚丙烯样品的红外谱图。其中曲线a为纯聚丙烯粉料的曲线，曲线b为实施例S1的微波辐照3min后得到的有机酸盐接枝聚丙烯的曲线，曲线c为实施例S2的微波辐照5min后得到的有机酸盐接枝聚丙烯的曲线。
对于所述有机酸盐接枝聚丙烯，只有一个酸盐峰，这是因为此时接枝在聚丙烯分子链的酸酐或者酸均成盐化，可以变成酸盐峰。从图2的红外谱图上可以看出接枝完毕并与氢氧化物反应后的接枝聚丙烯样品均具有羧酸基团，且微波时间的延长有助于接枝率的提升。
具体实施方式
下面结合实施例，进一步说明本发明。但是，本发明的范围不意于受这些实施例的限制，而是本发明的范围在附属的权利要求书中提出。
实施例和对比例中的实验数据用以下仪器设备及测定方法测定：
(1)实施例和对比例中树脂的熔融指数参照标准GB/T3682-2000进行测定。
(2)实施例和对比例中水接触角测定仪器是：德国EASYDROP接触角测试仪。
树脂的接触角测量样品的制备方法如下：将4g树脂溶于40ml二甲苯(分析纯AR)中，在120℃下使树脂充分溶于二甲苯；然后将树脂的二甲苯溶液倒入直径100mm的表面皿中制膜，将表面皿置于110℃烘箱中充分蒸发溶剂获得树脂膜样品；然后将树脂膜样品在乙醇中充分清洗并晾干即获得树脂的接触角测量样品。样品经过溶液法制膜过程会产生相分离，分散相是含极性单体(有机酸或有机酸盐)的一面，而另一面仅为聚丙烯。将所得接触角测量样品含极性单体侧基一面用上述水接触角测定仪器进行水接触角测定。
(3)实施例和对比例中极性单体(有机酸或有机酸盐)的接枝率如下通过红外光谱表征：
首先建立标准曲线。采用耐高温的十二烯基丁二酸酐(DDSA)与纯聚丙烯树脂以不同比例的混合样品为标样，测定十二烯基丁二酸酐中的酸酐羰基基团(C＝O基团)在1818-1755cm -1(峰尖位置约为1782cm -1)的红外吸收峰面积与聚丙烯内标峰在484-435cm -1(峰尖位置约为460cm -1)的吸收面积，由二者的比值对马来酸酐的含量作图，可得到接枝聚丙烯中马来酸酐接枝率的标准曲线。
接枝样品的接枝率的具体测试过程为：
A.对于实施例中和对比例中使用的微波接枝样品，由于在接枝完毕后，已使用去离子水充分去除未反应MAH单体，因此只需将样品在平板硫化机上(温度200℃)压制成厚度100μm左右的透明薄膜，然后用红外光谱仪(型号Nicolet iS 50，尼高力公司)测定特征吸收峰，然后通过上述标准曲线计算接枝率。
B.对比例中使用熔融法接枝的样品，测试过程如下：称取约1g的对比例得到的接枝聚丙烯样品，放入20ml二甲苯中，加热完全溶解后，立即倒入150ml丙酮中，未反应的小分子及未接枝于聚丙烯分子上的单体溶于丙酮，析出的白色絮状物即纯接枝物。将其过滤，干燥，然后在平板硫化机上(温度200℃)压制成厚度100μm左右的透明薄膜，用红外光谱仪测定特征吸收峰，然后通过上述标准曲线计算接枝率。本发明的有机酸盐接枝聚丙烯的接枝率可以等同于在有机酸接枝聚丙烯步骤得到的有机酸接枝聚丙烯的接枝率。
(4)所用的微波反应器为：SINEO(新仪)多功能微波合成萃取仪，型号：UWave-2000。
实施例和对比例中使用的原料及其生产厂商如下：
均聚聚丙烯粉料(镇海炼化M60，MI＝60g/10min，使用球形催化剂聚合得到)，无规共聚聚丙烯粉料(镇海炼化M60ET，MI＝60g/10min，使用球形催化剂聚合得到)、抗冲共聚聚丙烯粉料(镇海炼化M30RH，MI＝30g/10min，使用球形催化剂聚合得到)、马来酸酐(西陇科学股份有限公司)，丙烯酸(国药集团化学试剂有限公司)、甲基丙烯酸(国药集团化学试剂有限公司)、氯化钠(国药集团化学试剂有限公司)、氧化石墨烯(南京吉仓纳米科技有限公司)、抗坏血酸(百灵威公司)、(氢氧化钠(西陇科学股份有限公司)、氢氧化钾(西陇科学股份有限公司)、氢氧化钙(西陇科学股份有限公司)、丙酮(西陇科学股份有限公司)，过氧化二异丙苯(天津光复精细化工研究所)，抗氧剂1010(巴斯夫)、抗氧剂168(巴斯夫)、硬脂酸钙(天津津科精细化工研究所)。
实施例1：
按均聚聚丙烯粉料100质量份计，将马来酸酐(5质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将马来酸酐丙酮溶液在真空伴随机械搅拌的条件下加入到聚丙烯粉料中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射3min；微波照射完毕的粉料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后将粉料置于80℃鼓风干燥箱烘干。最后将粉料与0.1质量份(按均聚聚 丙烯粉料100质量份计)抗氧剂1010、0.1质量份抗氧剂168以及0.1质量份硬脂酸钙在双螺杆挤出机中熔融挤出造粒，挤出机加料段温度为190-200℃，混合段温度为200-210℃，机头温度为190-200℃，挤出造粒后进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例1’：
按均聚聚丙烯粉料100质量份计，将马来酸酐(5质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将氯化钠(3质量份)溶解在去离子水(50质量份)中得到氯化钠水溶液；将马来酸酐丙酮溶液在真空伴随机械搅拌的条件下加入到聚丙烯粉料中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的聚丙烯/马来酸酐混合物的粉料与氯化钠水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的聚丙烯/马来酸酐/氯化钠混合物的粉料在氮气气氛下微波(功率700W)照射2min；微波照射完毕的粉料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体和氯化钠，然后将粉料置于80℃鼓风干燥箱烘干。最后将粉料与0.1质量份(按均聚聚丙烯粉料100质量份计)抗氧剂1010、0.1质量份抗氧剂168以及0.1质量份硬脂酸钙在双螺杆挤出机中熔融挤出造粒，挤出机加料段温度为190-200℃，混合段温度为200-210℃，机头温度为190-200℃，挤出造粒后进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例1”
除将烘干后干燥的聚丙烯/马来酸酐/氯化钠混合物的粉料在氮气气氛下微波(功率700W)照射3min，其余均与实施例1’相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例1：
按均聚聚丙烯粉料(同实施例1)100质量份计，将马来酸酐(5质量份)与过氧化二异丙苯(0.005质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将马来酸酐丙酮溶液在真空伴随机械搅拌的条件下加入到聚丙烯粉料中充分混合，之后将混合物烘干(80摄氏度鼓风干燥烘箱烘干)。将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射3min；微波照射完毕的粉料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后将粉料置于80℃鼓风干燥箱烘干；最后将粉料与0.1质量份抗氧剂1010、0.1质量份抗氧剂168以及0.1质量份硬脂酸钙在双螺杆挤出机中熔融挤出造粒，挤出机加料段温度为190-200℃，混合 段温度为200-210℃，机头温度为190-200℃，挤出造粒后进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例2：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例2：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例3：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例3：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例4：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射10min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例4：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)照射10min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例5：
按均聚聚丙烯粉料(同实施例1)100质量份计，将过氧化二异丙苯(0.005质量份)溶解在丙酮(20质量份)中得到引发剂溶液；将马来酸酐(5质量份)与聚丙烯粉料在金属杯中使用搅拌桨进行固相干混，在混合过程中加入上述溶解好的过氧化物引发剂溶液。 最后将混合好的反应物与0.1质量份抗氧剂1010、0.1质量份抗氧剂168以及0.1质量份硬脂酸钙在双螺杆挤出机中熔融挤出造粒，挤出机加料段温度为190-200℃，混合段温度为200-210℃，机头温度为190-200℃，挤出造粒后进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例5：
除将马来酸酐(1质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例6：
除将马来酸酐(1质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例6：
除将马来酸酐(8质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例7：
除将马来酸酐(8质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例7：
除将马来酸酐(10质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例8：
除将马来酸酐(10质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例8：
除将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例9：
除将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例9：
除将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例10：
除将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射7min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例10：
除将甲基丙烯酸(5质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/甲基丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例11：
除将甲基丙烯酸(5质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/甲基丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例11：
除按抗冲共聚聚丙烯粉料100质量份计，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例11’：
除按抗冲共聚聚丙烯粉料100质量份计，将氧化石墨烯(0.5质量份)与抗坏血酸(0.5质量份)溶解在去离子水(50质量份)中得到氧化石墨烯水溶液；将烘干后干燥的聚丙烯/马来酸酐混合物的粉料与氧化石墨烯水溶液充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)；将烘干后干燥的聚丙烯/马来酸酐/氧化石墨烯混合物的粉料在氮气气氛下微波(功率700W)照射1min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例11”
除将烘干后干燥的聚丙烯/马来酸酐/氧化石墨烯混合物的粉料在氮气气氛下微波(功率700W)照射2min，其余均与实施例11’相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例12：
除按抗冲共聚聚丙烯粉料100质量份计，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例12：
除按抗冲共聚聚丙烯粉料100质量份计，将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例13：
除按抗冲共聚聚丙烯粉料100质量份计，将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例13：
除按无规共聚聚丙烯粉料100质量份计，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例14：
除按无规共聚聚丙烯粉料100质量份计，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
实施例14：
除按无规共聚聚丙烯粉料100质量份计，将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与实施例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
对比例15：
除按无规共聚聚丙烯粉料100质量份计，将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气气氛下微波(功率700W)照射5min，其余均与对比例1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表1。
表1
Figure PCTCN2019084622-appb-000001
从表1中可以看出，本发明的不添加引发剂的微波辐照下接枝聚丙烯的实施例，比通过添加引发剂的熔融共混接枝的聚丙烯的对比例的接枝率要高，而且聚丙烯接枝后的熔融 指数不升高，即分子量不下降，由此可见本发明实施例得到的极性单体接枝聚丙烯树脂的主链的断裂现象受到控制，保障了树脂的机械性能不受损失。另外可以看出，在加入过氧化物的微波辐照接枝的对比例中，即便在微波辐照接枝的条件下，由于过氧化物的加入，聚丙烯熔融指数升高得剧烈；并且由于存在接枝反应与自聚反应的竞争，在相同微波辐照时间下，不加过氧化物情况下所得样品的接枝率总高于添加过氧化物情况下所得样品的接枝率。接枝率越高，制膜后的水接触角越低。根据本发明的接枝聚丙烯由原料聚丙烯的不亲水性(接触角大于90°)改变为亲水性。
另外，可以看出，在额外添加无机微波吸收介质的情况下，可以进一步提高接枝聚丙烯的接枝率、降低水接触角和降低熔融指数。另外，与不添加无机微波吸收介质的情况相比，无机微波吸收介质的使用可以采用更短的微波辐照时间实现具有相似性能的接枝聚丙烯树脂，从而提高了生产效率。
实施例S1：
按均聚聚丙烯粉料100质量份计，将马来酸酐(5质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将氢氧化钠(5质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液；将马来酸酐丙酮溶液在真空伴随机械搅拌的条件下加入到聚丙烯粉料中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)辐照3min；微波辐照完毕的粉料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后将粉料置于80℃鼓风干燥箱烘干；将氢氧化钠水溶液在真空搅拌的条件下加入至烘干的马来酸酐接枝聚丙烯粉料中充分混合，氢氧化钠水溶液加入后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗粉料然后将粉料置于80℃鼓风干燥箱烘干。最后将粉料与0.1质量份(按均聚聚丙烯粉料100质量份计)抗氧剂1010、0.1质量份抗氧剂168以及0.1质量份硬脂酸钙在双螺杆挤出机中熔融挤出造粒，挤出机加料段温度为190-200℃，混合段温度为200-210℃，机头温度为190-200℃，挤出造粒后进行熔融指数、接触角以及接枝率的测试，测试结果见表2。
对比例S1：
按均聚聚丙烯粉料(同实施例S1)100质量份计，将马来酸酐(5质量份)与过氧化二异丙苯(0.005质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液；将氢氧化钠(5质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液；将马来酸酐丙酮溶 液在真空伴随机械搅拌的条件下加入到聚丙烯粉料中充分混合，之后将混合物烘干(80℃鼓风干燥烘箱烘干)。将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)辐照3min；微波辐照完毕的粉料在去离子水中浸泡10分钟并更换去离子水重复3遍以确保去除未参与接枝反应的马来酸酐单体，然后将粉料置于80℃鼓风干燥箱烘干；将氢氧化钠水溶液在真空搅拌的条件下加入至烘干的马来酸酐接枝聚丙烯粉料中充分混合，氢氧化钠水溶液加入后再搅拌混合并反应5分钟。反应完毕后使用去离子水按同上清洗步骤清洗粉料然后将粉料置于80℃鼓风干燥箱烘干。最后将粉料与0.1质量份抗氧剂1010、0.1质量份抗氧剂168以及0.1质量份硬脂酸钙在双螺杆挤出机中熔融挤出造粒，挤出机加料段温度为190-200℃，混合段温度为200-210℃，机头温度为190-200℃，挤出造粒后进行熔融指数、接触角以及接枝率的测试，测试结果见表2。
实施例S2：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)辐照5min，其余均与实施例S1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表2。
对比例S2：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气气氛下微波(功率700W)辐照5min，其余均与对比例S1相同。将样品进行熔融指数、接触角以及接枝率的测试，测试结果见表2。
实施例S3：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照7min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
对比例S3：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照7min，其余均与对比例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S4：
除将烘干后干燥的聚丙烯马来酸酐混合物的粉料在氮气气氛下微波(功率700W)辐照10min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试， 测试结果见表2。
对比例S4：
除将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照10min，其余均与对比例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S5：
除将氢氧化钠(1质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
对比例S5：
除将氢氧化钠(1质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与对比例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S6：
除将氢氧化钠(8质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
对比例S6：
除将氢氧化钠(8质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与对比例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S7：
除将氢氧化钠(10质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
对比例S7：
除将氢氧化钠(10质量份)溶解在去离子水(50质量份)中得到氢氧化钠水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与对比例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S8：
除将氢氧化钾(5质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
对比例S8：
除将氢氧化钾(5质量份)溶解在去离子水(50质量份)中得到氢氧化钾水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与对比例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S9：
除将氢氧化钙(5质量份)溶解在去离子水(50质量份)中得到氢氧化钙水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
对比例S9：
除将氢氧化钙(5质量份)溶解在去离子水(50质量份)中得到氢氧化钙水溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min,其余均与对比例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S10：
除将将马来酸酐(1质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照7min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S11：
除将将马来酸酐(8质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照7min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S12：
除将将马来酸酐(10质量份)溶解在丙酮(50质量份)中得到马来酸酐丙酮溶液，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照7min,其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S13：
除按抗冲共聚聚丙烯粉料100质量份计，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S14：
除按抗冲共聚聚丙烯粉料100质量份计，将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气的气氛下微波(功率700W)辐照5min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S15：
除按无规共聚聚丙烯粉料100质量份计，将烘干后干燥的聚丙烯/马来酸酐混合物的粉料在氮气的气氛下微波(功率700W)辐照5min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S16：
除按无规共聚聚丙烯粉料100质量份计，将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后干燥的聚丙烯/丙烯酸混合物的粉料在氮气的气氛下微波(功率700W)辐照5min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S17：
除将丙烯酸(5质量份)溶解在丙酮(50质量份)中得到丙烯酸丙酮溶液，将烘干后 干燥的聚丙烯/丙烯酸混合物的粉料在氮气的气氛下微波(功率700W)辐照5min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
实施例S18：
除将甲基丙烯酸(5质量份)溶解在丙酮(50质量份)中得到甲基丙烯酸丙酮溶液，将烘干后干燥的聚丙烯甲基丙烯酸混合物的粉料在氮气的气氛下微波(功率700W)辐照5min，其余均与实施例S1相同。将样品进行熔融指数，接触角以及接枝率的测试，测试结果见表2。
表2
Figure PCTCN2019084622-appb-000002
从表2中可以看出，本发明的不添加引发剂的微波辐照下有机酸盐接枝聚丙烯的实施例，比通过加引发剂的熔融共混接枝的聚丙烯的对比例的接枝率要高，而且聚丙烯接枝后的熔融指数不升高，即分子量不下降，由此可见本发明实施例得到的有机酸盐接枝聚丙烯树脂的主链的断裂现象受到控制，保障了树脂的机械性能不受损失。另外可以看出，在加入过氧化物的微波辐照接枝的对比例中，即便在微波辐照接枝的条件下，由于过氧化物的加入，聚丙烯熔融指数升高得剧烈；且由于存在接枝反应与自聚反应的竞争，在相同微波 辐照时间下，不加过氧化物情况下所得样品的接枝率总高于添加过氧化物情况下所得样品的接枝率。
从表2还可以看出，对于根据本发明的实施例的有机酸盐接枝聚丙烯，接枝率越高，制膜后的水接触角越低。本发明的有机酸盐接枝聚丙烯由原料聚丙烯的不亲水性(接触角大于90°)改变为亲水性，甚至接触角可达到0°。
另外，从表1和2的比较可以看出，在添加氢氧化物后，相同接枝率的有机酸盐接枝聚丙烯的水接触角明显小于有机酸接枝聚丙烯的水接触角，因此，氢氧化物的加入能够进一步提高接枝聚丙烯的极性。

Claims (33)

  1. 一种极性单体接枝聚丙烯树脂，其中所述接枝聚丙烯树脂内不含引发剂残留物，并且所述极性单体能够吸收微波从而使其在微波场中的温度升高至高于200℃。
  2. 根据权利要求1的接枝聚丙烯树脂，其特征在于所述接枝聚丙烯树脂的熔融指数小于或等于作为接枝基础物的所述聚丙烯树脂的熔融指数。
  3. 根据权利要求1或2的接枝聚丙烯树脂，其特征在于所述极性单体含有选自氧、硫、氮和卤素及其组合的杂原子或其取代基并且含有碳碳双键。
  4. 根据权利要求3的接枝聚丙烯树脂，其特征在于所述极性单体选自有机酸、有机酸的衍生物(例如酸酐、酯、盐)以及它们的组合，优选选自马来酸酐、马来酸酐衍生物、(甲基)丙烯酸、(甲基)丙烯酸衍生物(例如甲基丙烯酸缩水甘油酯)、乙酸乙烯酯、烯基磺酸及其衍生物、对苯乙烯甲酸、对苯乙烯乙酸、衣康酸、油酸、花生烯酸及其组合以及它们的成盐形式。
  5. 根据权利要求1-4中任一项的接枝聚丙烯树脂，其特征在于接枝率为0.01％-8％，优选0.01％-6％。
  6. 根据权利要求1-5中任一项的接枝聚丙烯树脂，其特征在于所述接枝聚丙烯树脂的水接触角数值小于90°，优选小于65°，更优选为50°-0°，对于由所述接枝聚丙烯树脂通过溶液法制得的膜测得。
  7. 根据权利要求1-6中任一项的接枝聚丙烯树脂，其特征在于作为接枝基础物的聚丙烯树脂选自丙烯均聚物和丙烯共聚物及其混合物，优选丙烯的无规共聚物，其中所述丙烯的无规共聚物中的共聚单体优选选自乙烯、除了丙烯以外的α-烯烃及其组合，更优选乙烯、C 4、C 5、C 6至C 8-α-烯烃及其组合，更优选所述丙烯的无规共聚物中只包含乙烯或一种除了丙烯以外的α-烯烃作为共聚单体。
  8. 根据权利要求7的接枝聚丙烯树脂，其特征在于作为接枝基础物的聚丙烯树脂是抗冲聚丙烯树脂，其除了包含丙烯均聚物外还包含橡胶相，所述橡胶相是由丙烯与选自乙烯、除了丙烯以外的α-烯烃中的至少一种，优选乙烯、C 4、C 5、C 6至C 8α-烯烃的共聚单体形成的共聚物，优选所述抗冲聚丙烯树脂的橡胶相是由丙烯与乙烯或一种除了丙烯以外的α-烯烃聚合而形成的。
  9. 根据权利要求1-8中任一项的接枝聚丙烯树脂，其特征在于作为接枝基础物的聚丙烯树脂是包括粉料、粒料或制品的固体形式，优选是使用球形催化剂聚合得到的聚丙烯粉料。
  10. 根据权利要求1-9中任一项的接枝聚丙烯树脂，其特征在于所述接枝聚丙烯树脂是通过将所述极性单体与固体聚丙烯树脂在不添加引发剂的情况下使用微波辐照进行接枝反应，任选地将接枝反应后所得产物进一步成盐得到的。
  11. 制备根据权利要求1-9中任一项的接枝聚丙烯树脂的方法，包括将所述极性单体与固体聚丙烯树脂在不添加引发剂的情况下使用微波辐照进行接枝反应的步骤。
  12. 根据权利要求11的方法，其特征在于所述极性单体的用量为基于固体聚丙烯树脂重量计的0.1-10％重量；优选1-8％重量。
  13. 根据权利要求11或12的方法，其特征在于所述极性单体为液体或溶液形式。
  14. 根据权利要求11-13中任一项的方法，其特征在于所述微波辐照的辐照功率为100w-2000w，优选500w-1000w；辐射时间为1s-120min，优选1min-30min。
  15. 根据权利要求11-14中任一项的方法，其特征在于所述方法包括以下步骤：
    1)将极性单体与固体聚丙烯树脂进行充分混合；
    2)对步骤1)中所得混合物进行微波辐照，优选在惰性气体气氛下进行。
  16. 根据权利要求15的方法，其特征在于步骤1)中极性单体与固体聚丙烯树脂在真 空条件下充分混合。
  17. 根据权利要求15或16的方法，其特征在于步骤2)中所述惰性气体选自氮气、氦气、氩气中的一种或多种。
  18. 根据权利要求15-17中任一项的方法，其特征在于所述极性单体为溶解在溶剂中的溶液形式，并且在步骤2)之前对步骤1)中所得混合物进行干燥以除去溶剂，所述溶剂优选选自醇、酮、酯、水中的至少一种，优选丙酮或乙醇。
  19. 根据权利要求15-18中任一项的方法，其特征在于将步骤2)中获得的辐照后的混合物进行清洗以除去未反应的极性单体，并进行干燥，用于清洗的溶剂优选选自醇、酮、酯、水中的至少一种，优选水。
  20. 根据权利要求11-19中任一项的方法，其特征在于使用的固体聚丙烯树脂不含抗氧剂。
  21. 根据权利要求11-20中任一项的方法，其特征在于所述极性单体是有机酸或其酸酐或酯，将在微波辐照下进行接枝反应后所得产物进一步与碱进行反应，更优选将有机酸接枝聚丙烯粉料与碱的水溶液在真空下充分混合反应，任选地使用溶剂清洗去除未反应的碱并进行干燥处理，从而得到有机酸盐接枝的聚丙烯树脂。
  22. 根据权利要求21的方法，其特征在于所述碱是氢氧化物，优选选自氨水和金属氢氧化物，例如氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物，优选选自氢氧化钠、氢氧化钾、氢氧化钡、氢氧化锂、氢氧化锶、氢氧化钙，及其组合。
  23. 根据权利要求21或22的方法，其特征在于所述碱的用量为基于所用聚丙烯树脂重量计的0.1-10％重量；优选1-8％重量。
  24. 根据权利要求11-23中任一项的方法，其特征在于在接枝反应过程中不使用辅助接枝单体。
  25. 根据权利要求11-24中任一项的方法，其特征在于添加无机微波吸收介质。
  26. 根据权利要求25的方法，其特征在于所述无机微波吸收介质的用量为基于固体聚丙烯树脂重量计的0.1-10％重量；优选为1-8％重量。
  27. 根据权利要求25或26的方法，其特征在于所述无机微波吸收介质选自金属氢氧化物，优选氢氧化钾、氢氧化钡、氢氧化钠、氢氧化锂、氢氧化锶、氢氧化钙、氢氧化铁、氢氧化亚铁、氢氧化锌、氢氧化镁、氢氧化钴、氢氧化金、氢氧化铝、氢氧化铜、氢氧化铍、稀土氢氧化物；金属盐，优选硝酸铵、硝酸钾、硝酸钠、硝酸钡、硝酸钙、硝酸镁、硝酸铝、硝酸锰、硝酸锌、硝酸铁、硝酸亚铁、硝酸铜、硝酸银、氯化铵、氯化钾、氯化钠、氯化钡、氯化钙、氯化镁、氯化铝、氯化锰、氯化锌、氯化铁、氯化亚铁、氯化铜、硫酸铵、硫酸钾、硫酸钠、硫酸钙、硫酸镁、硫酸铝、硫酸锰、硫酸锌、硫酸铁、硫酸亚铁、硫酸铜、硫酸银、碳酸铵、碳酸钾、碳酸钠、碳酸镁、碳酸钙、碳酸钡、磷酸二氢钾、钛酸钡、钛酸锶、钛酸铜钙；金属氧化物，优选三氧化二铁、四氧化三铁；石墨类材料，优选炭黑、石墨粉、氧化石墨烯及其还原产物、石墨烯、碳纳米管、活性炭；铁电类材料；电解石；黄铜矿；以及它们的组合。
  28. 根据权利要求25-27中任一项的方法，其特征在于在微波辐照之前，将任选地溶解于溶剂中的极性单体、任选地溶解或分散(优选添加表面活性剂的情况下)于溶剂中的无机微波吸收介质与固体聚丙烯树脂充分混合，优选在真空条件下进行，其中所述用于溶解极性单体的溶剂与用于溶解或分散无机微波吸收介质的溶剂相同或不同，优选选自水和有机溶剂，例如醇、酮、酯，任选地在混合后进行干燥处理以去除溶剂。
  29. 根据权利要求28的方法，其特征在于首先将所述聚丙烯树脂与任选地溶解于溶 剂中的极性单体混合，然后将形成的混合物与任选地溶解或分散于溶剂中的无机微波吸收介质混合。
  30. 根据权利要求25-29中任一项的方法，其特征在于将辐照后的混合物进行清洗以除去未反应的极性单体和任选地除去无机微波吸收介质，并进行干燥。
  31. 粒料或制品，其由根据权利要求1-10中任一项的接枝聚丙烯树脂或通过根据权利要求11-30中任一项的方法制备的接枝聚丙烯树脂，在任选添加添加剂的情况下通过熔融挤出造粒或进一步的成型工艺获得。
  32. 复合材料、可涂覆膜材料和粘接材料，其通过将根据权利要求1-10中任一项的接枝聚丙烯树脂或通过根据权利要求11-30中任一项的方法制备的接枝聚丙烯树脂与其他聚合物共混制得。
  33. 根据权利要求1-10中任一项的接枝聚丙烯树脂或通过根据权利要求11-30中任一项的方法制备的接枝聚丙烯树脂用于改性塑料的用途。
PCT/CN2019/084622 2018-04-27 2019-04-26 极性单体接枝聚丙烯树脂及其制备方法和应用 WO2019206288A1 (zh)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA3098221A CA3098221A1 (en) 2018-04-27 2019-04-26 Polar monomer grafted polypropylene resin, preparation method therefor and application thereof
JP2020560280A JP7447015B2 (ja) 2018-04-27 2019-04-26 極性モノマーグラフト化ポリプロピレン樹脂、およびその製造方法と応用
US17/051,069 US11926687B2 (en) 2018-04-27 2019-04-26 Polar monomer grafted polypropylene resin, preparation method therefor and application thereof
SG11202010438RA SG11202010438RA (en) 2018-04-27 2019-04-26 Polar monomer grafted polypropylene resin, preparation method therefor and application thereof
BR112020021939-8A BR112020021939A2 (pt) 2018-04-27 2019-04-26 resina de polipropileno enxertado com monômero polar, método para a preparação de uma resina de polipropileno enxertado, pelotas ou artigos, materiais compósitos, materiais de película revestível e materiais de ligação e uso da resina de polipropileno enxertada
EP19792130.7A EP3786202B1 (en) 2018-04-27 2019-04-26 Polar monomer grafted polypropylene resin, preparation method therefor and application thereof
CN201980026153.4A CN112055721A (zh) 2018-04-27 2019-04-26 极性单体接枝聚丙烯树脂及其制备方法和应用

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201810389343.XA CN110407981A (zh) 2018-04-27 2018-04-27 一种有机酸接枝聚丙烯树脂及其制备方法和应用
CN201810389343.X 2018-04-27
CN201810389316.2 2018-04-27
CN201810389316.2A CN110407962A (zh) 2018-04-27 2018-04-27 一种有机酸盐接枝聚丙烯树脂及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2019206288A1 true WO2019206288A1 (zh) 2019-10-31

Family

ID=68294389

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/084622 WO2019206288A1 (zh) 2018-04-27 2019-04-26 极性单体接枝聚丙烯树脂及其制备方法和应用

Country Status (8)

Country Link
US (1) US11926687B2 (zh)
EP (1) EP3786202B1 (zh)
JP (1) JP7447015B2 (zh)
CN (1) CN112055721A (zh)
BR (1) BR112020021939A2 (zh)
CA (1) CA3098221A1 (zh)
SG (1) SG11202010438RA (zh)
WO (1) WO2019206288A1 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112694567A (zh) * 2020-12-31 2021-04-23 宁波能之光新材料科技股份有限公司 一种微波辅助聚丙烯接枝的方法
CN112743945A (zh) * 2020-12-30 2021-05-04 中国科学院长春应用化学研究所 一种基于双连续结构的多层电磁屏蔽复合材料及其制备方法、应用
WO2021120450A1 (zh) * 2019-12-18 2021-06-24 武汉华星光电半导体显示技术有限公司 一种热活化延迟荧光绿光高分子材料及其制备方法
CN114103348A (zh) * 2021-11-22 2022-03-01 四川大学 多层复合bope电容膜及其制备方法
US11882757B2 (en) 2019-12-18 2024-01-23 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Thermally activated delayed fluorescence green polymer material and preparation method thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112158838B (zh) * 2020-10-25 2022-05-17 福州大学 一种氮氧共掺杂分级多孔碳材料的制备方法
CN112830997B (zh) * 2020-12-31 2022-08-09 石家庄联合石化有限公司 一种接枝改性聚丙烯的制备方法
CN113185654A (zh) * 2021-05-11 2021-07-30 泰兴盛嘉树脂有限公司 一种哑光羟基丙烯酸树脂的制备方法
CN113484271B (zh) * 2021-07-06 2023-07-04 绍兴文理学院 一种接枝蚕丝接枝率的定量分析方法
CN113698723B (zh) * 2021-09-30 2024-03-08 国网黑龙江省电力有限公司电力科学研究院 一种用于环保型电缆的聚丙烯基热塑型半导电屏蔽料及制备方法
CN114380951B (zh) * 2021-12-28 2023-09-26 金发科技股份有限公司 一种极性组分接枝聚丙烯材料及其制备方法和应用
CN114957554B (zh) * 2022-03-29 2024-05-17 合肥工业大学 基于二元接枝单体合成PEW-g-(MAH-co-DOM)微粉的方法
CN114752110A (zh) * 2022-04-21 2022-07-15 浙江沪天胶带有限公司 一种新型增塑剂的制备方法及其在制备pvc软管中的用途

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5585435A (en) 1994-09-26 1996-12-17 Pcd Polymere Gesellschaft M.B.H. Process for grafting polyolefins
US5612097A (en) * 1995-06-02 1997-03-18 The University Of Western Ontario, In Trust For Surface Science Western Plasma assisted grafting of maleic anhydride to polyolefins
CN1283642A (zh) 2000-08-30 2001-02-14 华南理工大学 聚烯烃与三单体固相接枝共聚物的制备方法及其应用
US6228948B1 (en) 1998-01-16 2001-05-08 E. I. Du Pont De Nemours And Company High melt flow, highly-grafted polypropylene
CN1482151A (zh) * 2003-06-12 2004-03-17 中国科学院长春应用化学研究所 功能化聚烯烃树脂的制备方法
CN1670049A (zh) * 2005-03-15 2005-09-21 华南理工大学 聚烯烃与乙烯基单体接枝共聚物的合成方法
CN1704436A (zh) 2004-05-31 2005-12-07 华东理工大学 一种聚烯烃连续固相接枝生产方法和装置
CN1821299A (zh) * 2006-03-24 2006-08-23 中国科学院长春应用化学研究所 一种功能化聚丙烯材料的制备方法
CN101668781A (zh) * 2007-04-27 2010-03-10 巴斯夫欧洲公司 借助微波辐射制备烯加合物的方法
CN102924661A (zh) 2012-11-15 2013-02-13 黄山贝诺科技有限公司 一种马来酸酐接枝聚丙烯材料
CN103102455A (zh) 2011-11-10 2013-05-15 中国石油化工股份有限公司 一种聚烯烃接枝方法
JP2015013988A (ja) * 2013-06-06 2015-01-22 三井化学株式会社 変性オレフィン系重合体の製造方法
CN104804143A (zh) 2015-05-14 2015-07-29 华东理工大学 一种马来酸酐接枝聚丙烯的制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1821299A (en) * 1929-05-08 1931-09-01 Charles E Ferreira Reclining seat
JPS5247500B2 (zh) 1972-09-05 1977-12-02
SU608813A1 (ru) 1977-01-11 1978-05-30 Московский Ордена Ленина И Ордена Трудового Красного Знамени Государственный Университет Имени М.В.Лононосова Способ получени привитых сополимеров
JPS5681323A (en) 1979-12-07 1981-07-03 Toyo Ink Mfg Co Ltd Production of polyolefin type resin
JP2732477B2 (ja) 1988-12-26 1998-03-30 三井化学株式会社 変性プロピレン系重合体
DE4022570A1 (de) 1990-07-16 1992-01-23 Basf Ag Gepfropfte, vernetzte und vernetzbare propylencopolymerisate
DE4308591A1 (de) 1993-03-18 1994-09-22 Basf Ag Gepfropfte Propylencopolymerisate
JPH07278327A (ja) 1994-04-07 1995-10-24 Tonen Chem Corp 高分子基材のグラフト化処理方法
JP4803617B2 (ja) * 2008-05-13 2011-10-26 住友ゴム工業株式会社 変性天然ゴム、変性天然ゴムの製造方法、ゴム組成物およびタイヤ
RU2430116C1 (ru) 2010-01-29 2011-09-27 Закрытое Акционерное Общество "Сибур Холдинг" Способ полимеризации и сополимеризации олефиновых олигомеров
JP2012125556A (ja) 2010-11-25 2012-07-05 Dic Corp ヒト免疫不全ウイルス除去或いは不活性化用高分子基材
JP2016003332A (ja) 2014-06-19 2016-01-12 ダイハツ工業株式会社 ポリプロピレン
CN111848873B (zh) 2019-04-26 2023-08-15 中国石油化工股份有限公司 一种功能单体接枝聚丙烯及其制备方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5585435A (en) 1994-09-26 1996-12-17 Pcd Polymere Gesellschaft M.B.H. Process for grafting polyolefins
US5612097A (en) * 1995-06-02 1997-03-18 The University Of Western Ontario, In Trust For Surface Science Western Plasma assisted grafting of maleic anhydride to polyolefins
US6228948B1 (en) 1998-01-16 2001-05-08 E. I. Du Pont De Nemours And Company High melt flow, highly-grafted polypropylene
CN1283642A (zh) 2000-08-30 2001-02-14 华南理工大学 聚烯烃与三单体固相接枝共聚物的制备方法及其应用
CN1482151A (zh) * 2003-06-12 2004-03-17 中国科学院长春应用化学研究所 功能化聚烯烃树脂的制备方法
CN1704436A (zh) 2004-05-31 2005-12-07 华东理工大学 一种聚烯烃连续固相接枝生产方法和装置
CN1670049A (zh) * 2005-03-15 2005-09-21 华南理工大学 聚烯烃与乙烯基单体接枝共聚物的合成方法
CN1821299A (zh) * 2006-03-24 2006-08-23 中国科学院长春应用化学研究所 一种功能化聚丙烯材料的制备方法
CN101668781A (zh) * 2007-04-27 2010-03-10 巴斯夫欧洲公司 借助微波辐射制备烯加合物的方法
CN103102455A (zh) 2011-11-10 2013-05-15 中国石油化工股份有限公司 一种聚烯烃接枝方法
CN102924661A (zh) 2012-11-15 2013-02-13 黄山贝诺科技有限公司 一种马来酸酐接枝聚丙烯材料
JP2015013988A (ja) * 2013-06-06 2015-01-22 三井化学株式会社 変性オレフィン系重合体の製造方法
CN104804143A (zh) 2015-05-14 2015-07-29 华东理工大学 一种马来酸酐接枝聚丙烯的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3786202A4

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021120450A1 (zh) * 2019-12-18 2021-06-24 武汉华星光电半导体显示技术有限公司 一种热活化延迟荧光绿光高分子材料及其制备方法
US11882757B2 (en) 2019-12-18 2024-01-23 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Thermally activated delayed fluorescence green polymer material and preparation method thereof
CN112743945A (zh) * 2020-12-30 2021-05-04 中国科学院长春应用化学研究所 一种基于双连续结构的多层电磁屏蔽复合材料及其制备方法、应用
CN112743945B (zh) * 2020-12-30 2022-05-06 中国科学院长春应用化学研究所 一种基于双连续结构的多层电磁屏蔽复合材料及其制备方法、应用
CN112694567A (zh) * 2020-12-31 2021-04-23 宁波能之光新材料科技股份有限公司 一种微波辅助聚丙烯接枝的方法
CN114103348A (zh) * 2021-11-22 2022-03-01 四川大学 多层复合bope电容膜及其制备方法

Also Published As

Publication number Publication date
US20210246248A1 (en) 2021-08-12
JP2021522388A (ja) 2021-08-30
US11926687B2 (en) 2024-03-12
EP3786202B1 (en) 2024-03-13
CA3098221A1 (en) 2019-10-31
SG11202010438RA (en) 2020-11-27
JP7447015B2 (ja) 2024-03-11
EP3786202A4 (en) 2022-03-30
EP3786202A1 (en) 2021-03-03
CN112055721A (zh) 2020-12-08
BR112020021939A2 (pt) 2021-03-02

Similar Documents

Publication Publication Date Title
WO2019206288A1 (zh) 极性单体接枝聚丙烯树脂及其制备方法和应用
CN111848873B (zh) 一种功能单体接枝聚丙烯及其制备方法
CN110407981A (zh) 一种有机酸接枝聚丙烯树脂及其制备方法和应用
KR910004490B1 (ko) 그라프트화 전구체 및 그 제조방법
KR20150070106A (ko) 박편화 흑연 유도체의 제조 방법 및 박편화 흑연·수지 복합 재료의 제조 방법
US4939209A (en) Unsaturated copolymer resin composite
JPH06102702B2 (ja) グラフト化前駆体及びその製造方法
RU2801281C2 (ru) Полипропиленовая смола с привитым полярным мономером, способ ее получения и ее применение
JP6514445B2 (ja) 変性オレフィン系重合体の製造方法
JPH01138214A (ja) グラフト樹脂組成物の製造方法
CN110407962A (zh) 一种有机酸盐接枝聚丙烯树脂及其制备方法和应用
EP2892933A2 (en) Disentangled ultra high molecular weight polyethylene graft copolymers and a process for preparation thereof
JP4705474B2 (ja) 変性オレフィン系重合体の製造方法
JPS6338047B2 (zh)
JPS5925806A (ja) 新規重合体組成物の製造法
WO2007097799A1 (en) Solid state modification of propylene polymers
JP6891663B2 (ja) 熱可塑性樹脂組成物およびその成形品
JPH0873540A (ja) 変性樹脂の製造方法
RU2020138669A (ru) Полипропиленовая смола с привитым полярным мономером, способ ее получения и ее применение
JPH05295047A (ja) グラフト重合体含有樹脂組成物の製法
DE3008747A1 (de) Verfahren zur herstellung von vernetzten pfropfcopolymerisaten
JPH0347642B2 (zh)
JPH10182735A (ja) 反応性基による窒素における置換スクシンイミド環を含むポリマー
JPS627736A (ja) エポキシ基グラフト化ポリオレフイン共重合体の製造法
JPS61111314A (ja) グラフト化エチレン−酢酸ビニル共重合体の製造法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19792130

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3098221

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2020560280

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112020021939

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2019792130

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 112020021939

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20201027