CN110407981A - A kind of organic acid grafted polypropylene resin and its preparation method and application - Google Patents
A kind of organic acid grafted polypropylene resin and its preparation method and application Download PDFInfo
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- CN110407981A CN110407981A CN201810389343.XA CN201810389343A CN110407981A CN 110407981 A CN110407981 A CN 110407981A CN 201810389343 A CN201810389343 A CN 201810389343A CN 110407981 A CN110407981 A CN 110407981A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The present invention relates to polypropylene grafted modified fields, provide a kind of organic acid grafted polypropylene resin and preparation method and application using microwave initiation.There are organic acid side groups on polypropylene molecule main chain in the organic acid grafted polypropylene resin, and noresidue organic acid monomer, grafting rate are 0.01%~8%.The present invention be prepared for molecular weight do not decline, noresidue monomer, no initiator residual, tasteless polarity grafted polypropylene resin.Preparation process of the present invention is simple, easy to operate, and preparation method and equipment are simple, at low cost to be easy to industrialize.
Description
Technical field
The invention belongs to polypropylene grafted technical field of modification, it is related to a kind of organic acid grafted polypropylene resin and its preparation
Methods and applications.
Background technique
Polypropylene is a kind of commodity polymer material having many uses, and has excellent physical and mechanical property.But poly- third
The nonpolarity and low-surface-energy of alkene, make the poor compatibility of it and most polymers and filler, are not easy to soak, bond, and print
Brush and paintability are poor, and performance preferable material can not be obtained when being blended with polar material.Therefore certain methods are needed to change
It is apt to polyacrylic polarity.Common method is maleic anhydride isopolarity monomer to be grafted in polypropylene backbone to improve its pole
Property.The method of graft modification mainly has solvent method, fusion method and solid phase method.
Solvent method grafting rate is higher, and reaction process temperature is relatively low.But organic solvent is usually toluene or dimethylbenzene,
Therefore post-process more complex, at high cost, environment friendly is poor, gradually eliminates in industrial practice.
Melt grafting is the current most reasonable approach, is suitble to industrialized production.Such as patent CN104804143A report
Be greater than the double screw extruder of 48:1 using draw ratio, multiple positions of the different barrel sections of extruder be added styrene and
The mixed solution of initiator obtains grafting rate height, and molecular weight connects without the maleic anhydride being substantially reduced compared with raw material polypropylene
Branch polypropylene.United States Patent (USP) US6,228,948 report in each section of double screw extruder use different technological parameter and condition,
Polypropylene, maleic anhydride are added in extruder, initiator, maleic anhydride reactive grafting to polypropylene molecule are added after melting
On chain, the polypropylene of 2% or more grafting rate, high comprehensive performance is obtained.Patent CN102924661A reports single using auxiliary
Body can be improved polypropylene grafted rate and inhibit polyacrylic degradation, while reduce maleic anhydride using new initiator
The penetrating odor of graft polypropylene, the initiator can also promote graft reaction degree and the copolymerization degree with auxiliary monomer, obtain
Obtain the maleic anhydride inoculated polypropylene that grafting rate is high, penetrating odor is low.
β chain-breaking reaction in polypropylene fusion graft process is unavoidable side reaction in grafting process, therefore is melted
The melt index of the maleic anhydride inoculated polypropylene product of Graft Method preparation is usually all very high, i.e., molecular weight is greatly reduced, this meeting
Polypropylene product mechanical property is caused to be deteriorated.Therefore the main problem that melt grafting is faced is how to obtain sufficiently high horse
While maleic anhydride grafted rate keep polypropylene matrix mechanical property, i.e., holding molecular weight be basically unchanged, in this way with other
Material is just unlikely to influence material final overall mechanical properties when being blended.
Solid phase method reaction temperature is in glass transition temperature of polymer hereinafter, reaction is carried out in exposed polypropylene surface.
Patent CN1283642A discloses the preparation method and application of a kind of polypropylene and composites, is by poly- third
Alkene, initiator and three kinds of monomers are put in proportion into reaction kettle, and interfacial agent dimethylbenzene is added, carries out solid phase under nitrogen atmosphere
Graft reaction.Patent CN103102455A discloses a kind of polyacrylic grafting method, by polypropylene, organic acid, interfacial activity
Agent is added in the reactor with stirring, and initiator is added after reaching reaction temperature, carries out solid state shear pulrerizing, and initiator is wax packet
Wrap up in peroxide microcapsules.CN1704436A discloses a kind of polypropylene continuous solid phase grafting production method and device, US5,
585,435 disclose a kind of production method that Solid Phase Graft Modification of Polypropylene is carried out on fluidized bed.Above two technology is all
Contacting efficiency by improving reactant and initiator obtains high grafting rate.
The method of above-described polypropylene grafted modification has the following disadvantages: molecular weight and molecular weight, there are monomer residue,
It is needed in modifying process using initiator, the problems such as product has taste or needs special installation.Since the application of polar polypropylene is wide
General and market is huge, and a kind of graft polypropylene cheap, that preparation method is simple and there is no disadvantages mentioned above becomes urgently to be resolved
Problem.To solve the above problems, proposing the present invention.
Summary of the invention
The present invention in order to overcome the shortcomings in the prior art, has invented a kind of organic acid graft polypropylene caused using microwave
Resin and its preparation method and application.Its main feature is that organic acid and polypropylene powder are subjected to graft reaction under microwave irradiation,
Initiator and auxiliary monomer are not added.β chain-breaking reaction can be greatly reduced in this method, and obtains that grafting rate is higher and molecular weight
Not reducing, tasteless, the remaining organic acid grafted polypropylene resin of no initiator.
An object of the present invention is to provide a kind of organic acid grafted polypropylene resin.
A kind of organic acid grafted polypropylene resin of the present invention, it is characterised in that on polypropylene molecule main chain there are
Machine acid side group, the grafting rate of the organic acid side group are 0.01%~8%, preferably 0.01%~6%, more preferable 0.01%~
3%, most preferably 0.01%~1.2%.
It includes that maleic anhydride side group, maleic anhydride derivative side group, acrylic acid side group, acrylic acid spread out that the organic acid, which surveys base,
At least one of biological side group, vinyl acetate side group, glycidyl methacrylate side group.
Organic acid grafted polypropylene resin of the present invention is film-made in caudacoria by solwution method containing organic acid group one side
Water contact angle numerical value less than 90 °, preferably smaller than 65 °.
The melt index of organic acid grafted polypropylene resin of the present invention is less than or equal to the acrylic resin
Melt index, that is to say, that its melt index is less than or equal to the melt index of raw material before the acrylic resin is grafted itself.
Polyacrylic β chain-breaking reaction is controlled organic acid graft polypropylene of the invention during the preparation process, and polypropylene will not occur
The phenomenon that molecular weight reduces, the melt index of graft polypropylene can be consistent with raw material polypropylene, or even be reduced.
The second object of the present invention is to provide the preparation method of organic acid grafted polypropylene resin of the present invention.
The preparation method of organic acid grafted polypropylene resin of the present invention is by by organic acid and polypropylene powder
Graft reaction is carried out using microwave irradiation to prepare the organic acid grafted polypropylene resin.Specifically includes the following steps:
1) organic acid monomer is dissolved in a solvent, obtains organic acid monomer solution.
2) polypropylene powder and the resulting organic acid monomer solution of step 1) are sufficiently mixed, are then dried.
3) by the resulting mixture of step 2) under atmosphere of inert gases microwave irradiation.
4) mixture after the irradiation of step 3) acquirement is cleaned using solvent, removes unreacted organic acid monomer and does
Dry processing obtains organic acid graft polypropylene powder.
Solvent in step 1) described above and step 4) can be selected from least one of water, organic solvent, and the two can
It is identical can also be different.
As long as the dosage of step 1) solvent described above, which can dissolve organic acid monomer, forms solution, preferably resulting
The amount of organic acid monomer solution can be totally submerged the polypropylene powder as raw material, and the two of being more convenient for is sufficiently mixed.Usually
The weight ratio of organic acid monomer and solvent can be in (0.1~100): 100, preferably (0.5~50): 100, more preferable (1~30):
100。
Further,
Preparation method of the present invention preferably includes step 5) on the basis of above step:
The powder that step 4) is obtained carries out melting extrusion granulation, obtains the pellet of organic acid grafted polypropylene resin.
Organic acid dosage is 0.1~10%wt of polypropylene dosage in preparation method of the invention；Preferably 1~8%wt.
Preparation method of the present invention, polypropylene powder described in step 1) are preferably the polypropylene for being not added with antioxidant
Powder.Usual acrylic resin raw material in the prior art all contains certain antioxidant, and antioxidant is to obtain after polymerization
Addition when the polypropylene powder melting extrusion arrived is granulated.Polypropylene powder of the invention is preferably obtained with polymerization also unmelted
Melt the polypropylene powder of extruding pelletization, powder at this time is free from antioxidant.
In preparation method of the present invention, the polypropylene powder can be used common various in the prior art
At least one of polypropylene powder, such as homopolypropylene, atactic copolymerized polypropene, impact copolymer polypropylene.
The polymerization technique of polypropylene powder of the invention is also all existing in the prior art.Polypropylene powder of the present invention is excellent
It is selected as the polypropylene powder polymerizeing using spheric catalyst, this polypropylene powder polymerizeing by spheric catalyst
Material, particle is spherical, and particle surface has many holes, therefore this kind of polypropylene powder has very big specific surface area,
The area contacted with organic acid is big, facilitates the graft product for obtaining higher grafting rate.
When polypropylene powder of the invention is atactic copolymerized polypropene, in the comonomer of the atactic copolymerized polypropene
It include at least one of ethylene or alpha-olefin comonomer in addition to propylene；Optimal ethylene, C4Alpha-olefin, C5Alpha-olefin, C6α-
Alkene is to C8Alpha-olefin, more preferable ethylene, 1- butylene, 1- heptene, 1- hexene and 1- octene, then more excellent ethylene and C4Alpha-olefin, then
More preferable ethylene and 1- butylene, most preferably ethylene.The comonomer in addition to propylene may include above-mentioned ethylene and/or α-alkene
The mixture of hydrocarbon comonomer is preferably only ethylene or a kind of 'alpha '-olefin monomers；In the most preferred embodiment, this is random altogether
Polypropylene contains only propylene and ethylene.
When polypropylene powder of the invention is impact copolymer polypropylene, the impact copolymer polypropylene removes equal containing propylene
Include also rubber phase outside polymers, rubber phase is polymerized by propylene and other comonomers, other comonomers for ethylene or
At least one of alpha-olefin；Optimal ethylene, C4Alpha-olefin, C5Alpha-olefin, C6Alpha-olefin is to C8Alpha-olefin, more preferable ethylene, 1-
Butylene, 1- heptene, 1- hexene and 1- octene, then more excellent ethylene and C4Alpha-olefin is even more preferably selected as ethylene and 1- butylene, optimal
It is selected as ethylene.The rubber phase of the impact copolymer polypropylene is preferably formed by propylene and ethylene or a kind of alpha-olefine polymerizing；Most
In preferred embodiment, which contains only the copolymer of propylene and ethylene.
Preparation method of the present invention, the organic acid in step 1) are selected from maleic anhydride, maleic anhydride derivative, propylene
One or more of acid, acrylic acid derivative, vinyl acetate, glycidyl methacrylate.It is preferred that maleic anhydride, Malaysia
Anhydride ester derivs, acrylic acid, acrylic acid derivative.More preferable maleic anhydride.
Preparation method of the present invention, solvent described in step 1) preferably include at least one of alcohol, ketone, ester, water, more
It is preferred that acetone or alcohol.
Polypropylene powder described in its step 2) of preparation method of the present invention and organic acid monomer solution preferably exist
It is sufficiently mixed under vacuum conditions.Vacuum be conducive to that organic acid mixes with polypropylene more sufficiently, particularly with hole
For polypropylene, promotes grafted monomers to enter in polypropylene hole, be more advantageous to graft reaction.
Various mixed methods in the prior art can be used sufficiently mix to organic acid and polypropylene powder in step 2)
It closes, it is preferred to use common agitating mode and mixing plant carry out.Wherein mixing plant can be for magnetic agitation, mechanical stirring etc. often
Advise agitating device.
Various conventional drying methods in the prior art can be used in drying in step 2), including but not limited to as air blast is dry
Dry, air drying etc..The temperature that preferred drying temperature does not make polypropylene generate melting is advisable, such as no more than 160 DEG C.
Preparation method of the present invention, the irradiation power of microwave irradiation described in step 3) are 100w~2000w, preferably
For 500~1000w, more preferable 600w~800w；Radiated time is 1s~120min, preferably 1min~30min, further preferably 3min
~10min.The microwave irradiation uses to carry out in existing various microwave reactors in the prior art.
Preparation method of the present invention, inert gas described in step 3) include one of nitrogen, helium, argon gas or
It is several, preferred nitrogen.
Preparation method of the present invention, solvent described in step 4) include at least one of alcohol, ketone, ester, water, preferably
Water.
The cleaning of the mixture after irradiation is not particularly limited in step 4), can be by remaining organic acid removal
Can, common cleaning method can be used.Such as in the event of high temperatures immediately using volume more than polypropylene powder after microwave
The solvent soaking certain time (such as 5-15 minutes), then using filter device remove excessive moisture；Repeatedly (ratio
Such as 2-6 times) it impregnates, the polypropylene powder that filtering is cleaned up.The dry same step 2 of step 4), can be used the prior art
In various conventional drying methods, including but not limited to such as forced air drying, air drying.Preferred drying temperature does not make polypropylene
The temperature for generating melting is advisable, such as no more than 160 DEG C
Preparation method of the present invention, melting extrusion granulation is using common molten in plastic processing in the step 5)
Melt extrusion equipment, by organic acid graft polypropylene powder by conventional melting extrusion equipment, carries out melting extrusion granulation and be made
The pellet of organic acid grafted polypropylene resin.
During the preparation process, the usual processing temperature of blending temperature, that is, acrylic resin of material, is both guaranteeing polypropylene
Resin is melted completely and is selected in the range of it will not be made to decompose.In addition, according to processing needs, it can be in organic acid graft polypropylene
Polyacrylic usual auxiliaries, such as antioxidant, plasticizer etc. are added by usual dosage in powder.
The third object of the present invention is to provide the application of organic acid grafted polypropylene resin of the present invention.
Organic acid grafted polypropylene resin of the invention can be in the extensive use in modifying plastics, including but not limited to by institute
State organic acid grafted polypropylene resin (pellet or powder) be blended with other polymers be made composite material, can coat membrane material and
Adhesives etc..Specifically, organic acid grafted polypropylene resin of the present invention can be used as polypropylene in modifying plastics
With expanding material when other polymers composite；Such as composite material, fiberglass reinforced polyene in inorganics filled polyolefin
Hydrocarbon composite material can coat in the materials such as membrane material and adhesives, improve inorganic material or other components and acrylic resin
Interfacial interaction, resulting material have excellent comprehensive performance, can be applied to automobile, tool and architectural engineering etc. neck
Domain.
The present invention uses organic acid and polypropylene powder is described organic to prepare using microwave irradiation progress graft reaction
Sour grafted polypropylene resin.It is using the mechanism of microwave irradiation graft reaction: the polypropylene powder is under microwave environment
Microwave (under microwave irradiation seldom or do not absorb microwave, therefore do not generate heat under microwave irradiation), the organic acid exists
It can heat up and generate free radicals under conditions of microwave, high temperature can also cause polypropylene molecular chain nearby and generate free radicals, therefore have
Graft reaction can sufficiently occur with polypropylene for machine acid, and then obtain organic acid graft polypropylene；And microwave grafting reaction simultaneously can
Polyacrylic β chain-breaking reaction when substantially fusion method being avoided to be grafted, does not reduce polyacrylic molecular weight, and product is made to keep excellent
Mechanical property.During the preparation process because being not added with initiator or helping grafted monomers, and can be by unreacted organic acid list
Body sufficiently removes, it is hereby achieved that molecular weight does not decline, noresidue monomer, no initiator residual, tasteless polarity are grafted and gather
Propylene.
Preparation process of the present invention is simple, easy to operate, and preparation method and equipment are simple, at low cost, is easy to industrialize.
Detailed description of the invention
Fig. 1 is embodiment 1 in preparation method of the present invention, the INFRARED SPECTRUM of the maleic anhydride inoculated polypropylene sample of embodiment 2
Figure.Wherein curve a is the curve of virgin pp powder, curve b be embodiment 1 microwave irradiation 3min after obtained maleic anhydride
The curve of graft polypropylene, curve c are the song of the maleic anhydride inoculated polypropylene obtained after the microwave irradiation 5min of embodiment 2
Line.
It is that polypropylene molecular chain is grafted on anhydride form when organic acid microwave irradiation graft polypropylene, by washing,
Part anhydride group open loop becomes acid, part or acid anhydrides.The polypropylene specimen finished is grafted as can be seen from Figure 1 to all have
Extension with anhydride group and carboxylic acid group, and microwave time facilitates the promotion of grafting rate.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.The scope of the present invention is not restricted by the embodiments, this hair
Bright range proposes in the dependent claims.
The following instrument and equipment of experimental data and measuring method measurement in embodiment:
(1) the melt index determination method of resin is carried out referring to GB/T3682-2000 in the embodiment of the present invention and comparative example
Measure
(2) water contact angle measurement instrument is in the embodiment of the present invention and comparative example: German EASYDROP contact angle tester.
The contact angle sample preparation methods of resin are as follows: 4g resin being dissolved in 40ml dimethylbenzene, is sufficiently made at 120 DEG C
Resin is dissolved in dimethylbenzene, then pours into the xylene solution of resin in the surface plate of diameter 100mm and is film-made, surface plate is placed in
Solvent is sufficiently evaporated in 110 DEG C of baking ovens and obtains resin film sample, resin is sufficiently cleaned in ethanol then and is dried obtains
The contact angle sample of resin.Sample can be generated by solwution method film and mutually be separated, and dispersed phase is the one side containing acylate, and another
Become on one side is only polypropylene.The gained contact angle sample one side of side group containing organic acid is carried out with above-mentioned water contact angle measurement instrument
Water contact angle measurement.
(3) the grafting rate infrared spectrum characterization method of organic acid is as follows in the embodiment of the present invention and comparative example:
Initially set up standard curve.Not using dodecenylsuccinic acid acid anhydride (DDSA) resistant to high temperature and virgin pp resin
Mixing sample is standard specimen in proportion, measures the anhydride group (C=O group) in dodecenylsuccinic acid acid anhydride in 1818-1755cm-
In 484-435cm-1, (peak point position is about with polypropylene internal standard peak for the infrared absorption peak area of 1 (peak point position is about 1782cm-1)
For the absorption area of 460cm-1), is mapped by the ratio of the two to the content of maleic anhydride, Malaysia in graft polypropylene can be obtained
The standard curve of acid anhydrides grafting rate.
The specific test process of grafting samples are as follows:
A. in embodiment and comparative example used in microwave grafting sample, due to having used deionization after grafting
Water sufficiently removes unreacted MAH monomer, therefore only need to (200 DEG C of temperature) is pressed into 100 μ of thickness on vulcanizing press by sample
Then the transparent membrane of m or so calculates grafting rate by standard curve with determination of infrared spectroscopy characteristic absorption peak.
B. the sample being grafted in comparative example using fusion method, test process is as follows: weigh that the comparative example of about 1g obtains connects
Branch polypropylene specimen, is put into 20ml dimethylbenzene, after heating is completely dissolved, is poured into 150ml acetone immediately, unreacted small point
The sub and non-grafted monomer on macromolecule is dissolved in acetone, White Flocculus, that is, pure graft of precipitation.After being filtered, being dry
(200 DEG C of temperature) is pressed into 100 μm of thickness or so of transparent membrane on vulcanizing press, is inhaled with determination of infrared spectroscopy feature
Peak is received, grafting rate is then calculated by standard curve.
(4) introduction of microwave reactor is briefly supplemented
SINEO (new instrument) multifunction microwave synthesizes abstraction instrument, model: UWave-2000.
Raw material used in this patent embodiment and comparative example and its production firm are as follows:
Homo-polypropylene powder (Zhenghai refinery M60, MI=60g/10min, spheric catalyst polymerize to obtain), random copolymerization
Polypropylene powder (Zhenghai refinery M60ET, MI=60g/10min, spheric catalyst polymerize to obtain), impact copolymer polypropylene powder
(Zhenghai refinery M30RH, MI=30g/10min, spheric catalyst polymerize to obtain), maleic anhydride (the western limited public affairs of Gansu Province science share
Department), acrylic acid (Sinopharm Chemical Reagent Co., Ltd.), methacrylic acid (Sinopharm Chemical Reagent Co., Ltd.), third
Ketone (western Gansu Province science limited liability company), cumyl peroxide (fine chemistry industry research institute is recovered in Tianjin), antioxidant 1010 (bar
Si Fu), irgasfos 168 (BASF), calcium stearate (Tianjin Jin Ke fine chemistry industry research institute).
Embodiment 1:
Based on 100 mass parts of homo-polypropylene powder, maleic anhydride (5 mass parts) is dissolved in acetone (50 mass parts)
Obtain maleic anhydride acetone soln；Maleic anhydride acetone soln is added to polypropylene under conditions of vacuum is with mechanical stirring
It is sufficiently mixed in powder, later by mixture drying (80 DEG C of blast dry oven drying).The polypropylene horse that will be dried after drying
Carry out the powder of acid anhydride mixture microwave (power 700W) 3min under the atmosphere of nitrogen；The powder that microwave finishes is in deionized water
It impregnates 10 minutes and replaces deionized water and repeat 3 times to ensure that removal has neither part nor lot in the maleic anhydride monomer of graft reaction, then will
Powder is placed in 80 DEG C of air dry oven drying.Finally by powder and 0.1 mass parts (based on 100 mass parts of homo-polypropylene powder)
Antioxidant 1010,0.1 mass parts irgasfos 168 and 0.1 mass parts calcium stearate melting extrusion in double screw extruder are made
Grain, extruder feeding section temperature are 190~200 DEG C, and mixing section temperature is 200~210 DEG C, and head temperature is 190~200 DEG C,
Melt index, the test of contact angle and grafting rate are carried out after extruding pelletization, test result is shown in Table 1.
Comparative example 1:
Based on 100 mass parts of homo-polypropylene powder (with embodiment 1), by maleic anhydride (5 mass parts) and peroxidating two
Isopropylbenzene (0.005 mass parts) is dissolved in acetone (50 mass parts) and obtains maleic anhydride acetone soln；By maleic anhydride acetone
Solution is added in polypropylene powder under conditions of vacuum is with mechanical stirring and is sufficiently mixed, and mixture is dried (80 later
Degree Celsius blast dry oven drying).By the powder for the polypropylene maleic anhydride mixture dried after drying nitrogen atmosphere
Lower microwave (power 700W) 3min；The powder that microwave finishes, which impregnates 10 minutes in deionized water and replaces deionized water, repeats 3
All over to ensure to remove the maleic anhydride monomer for having neither part nor lot in graft reaction, powder is then placed in 80 DEG C of air dry oven drying；Most
Afterwards by powder and 0.1 mass parts antioxidant 1010,0.1 mass parts irgasfos 168 and 0.1 mass parts calcium stearate in twin-screw
Melting extrusion is granulated in extruder, and extruder feeding section temperature is 190~200 DEG C, and mixing section temperature is 200~210 DEG C, head
Temperature is 190~200 DEG C, melt index, the test of contact angle and grafting rate is carried out after extruding pelletization, test result is shown in Table 1.
Embodiment 2:
Except the powder of polypropylene maleic anhydride mixture that will be dried after drying under the atmosphere of nitrogen microwave (power
700W) 5min, remaining is same as Example 1.Sample is subjected to melt index, the test of contact angle and grafting rate, test
It the results are shown in Table 1.
Comparative example 2:
Except the powder of polypropylene maleic anhydride mixture that will be dried after drying under the atmosphere of nitrogen microwave (power
700W) 5min, remaining is identical as comparative example 1.Sample is subjected to melt index, the test of contact angle and grafting rate, test
It the results are shown in Table 1.
Embodiment 3:
Except the powder of polypropylene maleic anhydride mixture that will be dried after drying under the atmosphere of nitrogen microwave (power
700W) 7min, remaining is same as Example 1.Sample is subjected to melt index, the test of contact angle and grafting rate, test
It the results are shown in Table 1.
Comparative example 3:
Except the powder of polypropylene maleic anhydride mixture that will be dried after drying under the atmosphere of nitrogen microwave (power
700W) 7min, remaining is identical as comparative example 1.Sample is subjected to melt index, the test of contact angle and grafting rate, test
It the results are shown in Table 1.
Embodiment 4:
Except the powder of polypropylene maleic anhydride mixture that will be dried after drying under the atmosphere of nitrogen microwave (power
700W) 10min, remaining is same as Example 1.Sample is subjected to melt index, the test of contact angle and grafting rate, test
It the results are shown in Table 1.
Comparative example 4:
Except the powder of polypropylene maleic anhydride mixture that will be dried after drying under the atmosphere of nitrogen microwave (power
700W) 10min, remaining is identical as comparative example 1.Sample is subjected to melt index, the test of contact angle and grafting rate, test
It the results are shown in Table 1.
Comparative example 5:
Based on 100 mass parts of homo-polypropylene powder (with embodiment 1), by cumyl peroxide (0.005 mass parts)
It is dissolved in acetone (20 mass parts) and obtains initiator solution；By maleic anhydride (5 mass parts) and polypropylene powder in metal cup
It is middle dry-mixed using agitating paddle progress solid phase, the good peroxide initiator solution of above-mentioned dissolution is added in mixed process.Finally
By the reactant mixed and 0.1 mass parts antioxidant 1010,0.1 mass parts irgasfos 168 and 0.1 mass parts calcium stearate
In double screw extruder melting extrusion be granulated, extruder feeding section temperature be 190~200 DEG C, mixing section temperature be 200~
210 DEG C, head temperature is 190~200 DEG C, and the test of melt index, contact angle and grafting rate, test are carried out after extruding pelletization
It the results are shown in Table 1.
Embodiment 5:
Maleic anhydride acetone soln is obtained except maleic anhydride (1 mass parts) to be dissolved in acetone (50 mass parts), will be dried
The powder of dry polypropylene maleic anhydride mixture microwave (power 700W) 7min under the atmosphere of nitrogen after dry, remaining with
Embodiment 1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Comparative example 6:
Maleic anhydride acetone soln is obtained except maleic anhydride (1 mass parts) to be dissolved in acetone (50 mass parts), will be dried
The powder of dry polypropylene maleic anhydride mixture microwave (power 700W) 7min under the atmosphere of nitrogen after dry, remaining with
Comparative example 1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Embodiment 6:
Maleic anhydride acetone soln is obtained except maleic anhydride (8 mass parts) to be dissolved in acetone (50 mass parts), will be dried
The powder of dry polypropylene maleic anhydride mixture microwave (power 700W) 7min under the atmosphere of nitrogen after dry, remaining with
Embodiment 1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Comparative example 7:
Maleic anhydride acetone soln is obtained except maleic anhydride (8 mass parts) to be dissolved in acetone (50 mass parts), will be dried
The powder of dry polypropylene maleic anhydride mixture microwave (power 700W) 7min under the atmosphere of nitrogen after dry, remaining with
Comparative example 1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Embodiment 7:
Maleic anhydride acetone soln is obtained except maleic anhydride (10 mass parts) to be dissolved in acetone (50 mass parts), will be dried
The powder of dry polypropylene maleic anhydride mixture microwave (power 700W) 7min under the atmosphere of nitrogen after dry, remaining with
Embodiment 1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Comparative example 8:
Maleic anhydride acetone soln is obtained except maleic anhydride (10 mass parts) to be dissolved in acetone (50 mass parts), will be dried
The powder of dry polypropylene maleic anhydride mixture microwave (power 700W) 7min under the atmosphere of nitrogen after dry, remaining with
Comparative example 1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Embodiment 8:
Acrylic acid acetone soln is obtained except acrylic acid (5 mass parts) to be dissolved in acetone (50 mass parts), after drying
The powder of dry polypropylene acrylic acid mixture microwave (power 700W) 5min under the atmosphere of nitrogen, remaining is and embodiment
1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Comparative example 9:
Acrylic acid acetone soln is obtained except acrylic acid (5 mass parts) to be dissolved in acetone (50 mass parts), after drying
The powder of dry polypropylene acrylic acid mixture microwave (power 700W) 5min under the atmosphere of nitrogen, remaining is and comparative example
1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Embodiment 9:
Acrylic acid acetone soln is obtained except acrylic acid (5 mass parts) to be dissolved in acetone (50 mass parts), after drying
The powder of dry polypropylene acrylic acid mixture microwave (power 700W) 7min under the atmosphere of nitrogen, remaining is and embodiment
1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Comparative example 10:
Acrylic acid acetone soln is obtained except acrylic acid (5 mass parts) to be dissolved in acetone (50 mass parts), after drying
The powder of dry polypropylene acrylic acid mixture microwave (power 700W) 7min under the atmosphere of nitrogen, remaining is and comparative example
1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Embodiment 10:
Methacrylic acid acetone soln is obtained except methacrylic acid (5 mass parts) to be dissolved in acetone (50 mass parts),
By the powder for the polypropylene metering system acid blend dried after drying under the atmosphere of nitrogen microwave (power 700W) 5min,
Yu Jun is same as Example 1.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Comparative example 11:
Methacrylic acid acetone soln is obtained except methacrylic acid (5 mass parts) to be dissolved in acetone (50 mass parts),
By the powder for the polypropylene metering system acid blend dried after drying under the atmosphere of nitrogen microwave (power 700W) 5min,
Yu Junyu comparative example 1 is identical.Sample is subjected to melt index, the test of contact angle and grafting rate, test result is shown in Table 1.
Embodiment 11:
Except the polypropylene maleic anhydride mixture that based on 100 mass parts of impact copolymer polypropylene powder, will be dried after drying
Powder under the atmosphere of nitrogen microwave (power 700W) 5min, remaining is same as Example 1.Sample is carried out melting to refer to
Number, the test of contact angle and grafting rate, test result are shown in Table 1.
Comparative example 12:
Except the polypropylene maleic anhydride mixture that based on 100 mass parts of impact copolymer polypropylene powder, will be dried after drying
Powder under the atmosphere of nitrogen microwave (power 700W) 5min, remaining is identical as comparative example 1.Sample is carried out melting to refer to
Number, the test of contact angle and grafting rate, test result are shown in Table 1.
Embodiment 12:
Except based on 100 mass parts of impact copolymer polypropylene powder, acrylic acid (5 mass parts) is dissolved in acetone (50 mass
Part) in obtain acrylic acid acetone soln, by the powder for the polypropylene acrylic acid mixture dried after drying under the atmosphere of nitrogen
Microwave (power 700W) 5min, remaining is same as Example 1.Sample is subjected to melt index, contact angle and grafting rate
Test, test result are shown in Table 1.
Comparative example 13:
Except based on 100 mass parts of impact copolymer polypropylene powder, acrylic acid (5 mass parts) is dissolved in acetone (50 mass
Part) in obtain acrylic acid acetone soln, by the powder for the polypropylene acrylic acid mixture dried after drying under the atmosphere of nitrogen
Microwave (power 700W) 5min, remaining is identical as comparative example 1.Sample is subjected to melt index, contact angle and grafting rate
Test, test result are shown in Table 1.
Embodiment 13:
Except the polypropylene maleic anhydride mixture that based on 100 mass parts of atactic copolymerized polypropene powder, will be dried after drying
Powder under the atmosphere of nitrogen microwave (power 700W) 5min, remaining is same as Example 1.Sample is carried out melting to refer to
Number, the test of contact angle and grafting rate, test result are shown in Table 1.
Comparative example 14:
Except the polypropylene maleic anhydride mixture that based on 100 mass parts of atactic copolymerized polypropene powder, will be dried after drying
Powder under the atmosphere of nitrogen microwave (power 700W) 5min, remaining is identical as comparative example 1.Sample is carried out melting to refer to
Number, the test of contact angle and grafting rate, test result are shown in Table 1.
Embodiment 14:
Except based on 100 mass parts of atactic copolymerized polypropene powder, acrylic acid (5 mass parts) is dissolved in acetone (50 mass
Part) in obtain acrylic acid acetone soln, by the powder for the polypropylene acrylic acid mixture dried after drying under the atmosphere of nitrogen
Microwave (power 700W) 5min, remaining is same as Example 1.Sample is subjected to melt index, contact angle and grafting rate
Test, test result are shown in Table 1.
Comparative example 15:
Except based on 100 mass parts of atactic copolymerized polypropene powder, acrylic acid (5 mass parts) is dissolved in acetone (50 mass
Part) in obtain acrylic acid acetone soln, by the powder for the polypropylene acrylic acid mixture dried after drying under the atmosphere of nitrogen
Microwave (power 700W) 5min, remaining is identical as comparative example 1.Sample is subjected to melt index, contact angle and grafting rate
Test, test result are shown in Table 1.
Table 1
From table 1 it follows that under the microwave irradiation for not adding initiator of the invention graft polypropylene embodiment, than
Want high by the polyacrylic grafting rate for adding the melt blending of initiator to be grafted, and it is polypropylene grafted after melt index not under
Drop, it is seen that the phenomenon of rupture of the main chain for the organic acid grafted polypropylene resin that the embodiment of the present invention obtains is controlled, and is ensured
The mechanical performance of resin is not suffered a loss.And it can be seen that in the comparative example of microwave irradiation grafting that peroxide is added, i.e.,
Just under conditions of microwave irradiation is grafted, due to the participation of peroxide, polypropylene melting means declines violent；And exist grafting with
The Competition of autohemagglutination, therefore the sample under identical microwave irradiation time, the sample grafting rate that peroxide is not added, which is always higher than, to be added
Add the sample of peroxide.Grafting rate is higher, film after water contact angle it is lower, graft polypropylene by the not hydrophilic of raw material
(contact angle is greater than 90 °) changes into hydrophily.
Claims (22)
1. a kind of organic acid grafted polypropylene resin, it is characterised in that there are organic acid sides on the molecular backbone of acrylic resin
Base, the grafting rate of the organic acid side group are 0.01%~8%, preferably 0.01%~6%.
2. organic acid grafted polypropylene resin according to claim 1, it is characterised in that the organic acid graft polypropylene
Organic acid side group on its main chain of resin includes maleic anhydride side group, maleic anhydride derivative side group, acrylic acid side group, acrylic acid
At least one of derivative side group, vinyl acetate side group, glycidyl methacrylate side group.
3. organic acid grafted polypropylene resin according to claim 1, it is characterised in that the organic acid graft polypropylene
Resin is less than 90o, preferably smaller than 65o by the water contact angle numerical value that solwution method is film-made the one side containing organic acid group in caudacoria.
4. organic acid grafted polypropylene resin according to claim 1, it is characterised in that the organic acid graft polypropylene
Resin melting index is less than or equal to the melt index of the acrylic resin.
5. organic acid grafted polypropylene resin described according to claim 1~one of 4, it is characterised in that the organic acid grafting
Acrylic resin is obtained by the way that organic acid and polypropylene powder are carried out graft reaction using microwave irradiation.
6. a kind of preparation method of organic acid grafted polypropylene resin described according to claim 1~one of 5, including pass through by
Organic acid and polypropylene powder carry out graft reaction using microwave irradiation and prepare the organic acid grafted polypropylene resin.
7. preparation method according to claim 6, it is characterised in that the following steps are included:
1) organic acid monomer is dissolved in a solvent, obtains organic acid monomer solution；
2) polypropylene powder and the resulting organic acid monomer solution of step 1) are sufficiently mixed, are then dried；
3) by the resulting mixture of step 2) under atmosphere of inert gases microwave irradiation；
4) mixture after the irradiation of step 3) acquirement is cleaned using solvent, is removed at unreacted organic acid monomer and drying
Reason, obtains the powder of organic acid grafted polypropylene resin；
The solvent of step 1) described above and step 4) is selected from least one of water, organic solvent, step 1) and step 4)
Solvent is identical or not identical.
8. preparation method according to claim 7, it is characterised in that include the following steps 5):
The powder that the step 4) is obtained carries out melting extrusion granulation, obtains the pellet of organic acid grafted polypropylene resin.
9. preparation method according to claim 6 or 7, it is characterised in that wherein the polypropylene powder is to be urged using spherical shape
The polypropylene powder that agent polymerize.
10. preparation method according to claim 6 or 7, it is characterised in that wherein the polypropylene powder is free of antioxygen
Agent.
11. preparation method according to claim 6 or 7, it is characterised in that:
The polypropylene powder is atactic copolymerized polypropene, includes in addition to propylene in the comonomer of the atactic copolymerized polypropene
There are at least one of ethylene or alpha-olefin comonomer；Optimal ethylene, C4Alpha-olefin, C5Alpha-olefin, C6Alpha-olefin is to C8α-alkene
Hydrocarbon.
12. preparation method according to claim 11, it is characterised in that:
The comonomer of the atactic copolymerized polypropene is in addition to propylene only comprising ethylene or a kind of alpha-olefin as comonomer.
13. preparation method according to claim 6 or 7, it is characterised in that:
The polypropylene powder is impact copolymer polypropylene, and the impact copolymer polypropylene is removed also includes containing propylene homo beyond the region of objective existence
Rubber phase, rubber phase are polymerized by propylene and other comonomers, other comonomers be in ethylene or alpha-olefin extremely
Few one kind；Optimal ethylene, C4Alpha-olefin, C5Alpha-olefin, C6Alpha-olefin is to C8Alpha-olefin.
14. preparation method according to claim 13, it is characterised in that:
The rubber phase of the impact copolymer polypropylene is formed by propylene and ethylene or a kind of alpha-olefine polymerizing.
15. preparation method according to claim 6 or 7, it is characterised in that:
Wherein the organic acid is selected from maleic anhydride, maleic anhydride derivative, acrylic acid, acrylic acid derivative, vinyl acetate, first
One or more of base glycidyl acrylate.
16. preparation method according to claim 6 or 7, it is characterised in that organic acid dosage be polypropylene dosage 0.1~
10%wt；Preferably 1~8%wt.
17. preparation method according to claim 7, it is characterised in that the step 1) solvent include alcohol, ketone, ester, in water
At least one, preferably acetone or alcohol.
18. preparation method according to claim 7, it is characterised in that polypropylene powder described in step 2) and organic acid
Monomer solution is sufficiently mixed under vacuum conditions.
19. preparation method according to claim 7, it is characterised in that the irradiation power of microwave irradiation described in step 3) is
100w~2000w, preferably 500w~1000w；Radiated time is 1s~120min, preferably 1min~30min.
20. preparation method according to claim 7, it is characterised in that inert gas described in step 3) includes nitrogen, helium
One or more of gas, argon gas.
21. preparation method according to claim 7, it is characterised in that solvent described in step 4) includes alcohol, ketone, ester, water
At least one of, preferred water.
22. application of described in any item organic acid grafted polypropylene resins in modified plastics according to claim 1~5, packet
It includes for the organic acid grafted polypropylene resin to be blended with other polymers and composite material is made, membrane material and Nian Jie material can be coated
Material.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810389343.XA CN110407981A (en) | 2018-04-27 | 2018-04-27 | A kind of organic acid grafted polypropylene resin and its preparation method and application |
| US17/051,069 US11926687B2 (en) | 2018-04-27 | 2019-04-26 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| CA3098221A CA3098221A1 (en) | 2018-04-27 | 2019-04-26 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| PCT/CN2019/084622 WO2019206288A1 (en) | 2018-04-27 | 2019-04-26 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| JP2020560280A JP7447015B2 (en) | 2018-04-27 | 2019-04-26 | Polar monomer-grafted polypropylene resin, its manufacturing method and application |
| SG11202010438RA SG11202010438RA (en) | 2018-04-27 | 2019-04-26 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| CN201980026153.4A CN112055721A (en) | 2018-04-27 | 2019-04-26 | Polar monomer grafted polypropylene resin and preparation method and application thereof |
| EP19792130.7A EP3786202B1 (en) | 2018-04-27 | 2019-04-26 | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| BR112020021939-8A BR112020021939A2 (en) | 2018-04-27 | 2019-04-26 | polypropylene resin grafted with polar monomer, method for preparing a grafted polypropylene resin, pellets or articles, composite materials, coated film materials and bonding materials and use of the grafted polypropylene resin |
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| CN112079962A (en) * | 2020-09-21 | 2020-12-15 | 哈尔滨理工大学 | Oil-resistant polyolefin elastomer graft and preparation method thereof |
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| CN113563525A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Application of graft modified polypropylene as insulating material and insulating material |
| CN113999344A (en) * | 2021-10-26 | 2022-02-01 | 中国石油化工股份有限公司 | Metallocene catalyzed alpha-olefin polymer grafted polypropylene and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113563525A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Application of graft modified polypropylene as insulating material and insulating material |
| CN112079962A (en) * | 2020-09-21 | 2020-12-15 | 哈尔滨理工大学 | Oil-resistant polyolefin elastomer graft and preparation method thereof |
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| CN113999344A (en) * | 2021-10-26 | 2022-02-01 | 中国石油化工股份有限公司 | Metallocene catalyzed alpha-olefin polymer grafted polypropylene and preparation method thereof |
| CN113999344B (en) * | 2021-10-26 | 2024-05-17 | 中国石油化工股份有限公司 | Metallocene-catalyzed alpha-olefin polymer grafted polypropylene and preparation method thereof |
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