CN108192027A - A kind of polar polypropylene graft and preparation method thereof - Google Patents
A kind of polar polypropylene graft and preparation method thereof Download PDFInfo
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- CN108192027A CN108192027A CN201711395770.0A CN201711395770A CN108192027A CN 108192027 A CN108192027 A CN 108192027A CN 201711395770 A CN201711395770 A CN 201711395770A CN 108192027 A CN108192027 A CN 108192027A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
Abstract
The invention discloses a kind of polar polypropylene graft, including following components by weight：100 parts of PP resin raw materials；0.1 5 parts of initiator monomer；02 parts of initiator；05 parts of polar monomer；It is grafted 05 parts of auxiliary agent；0.05 1 parts of antioxidant.The invention also discloses the preparation methods of polar polypropylene graft.The polar polypropylene graft of the present invention is to be prepared by introducing initiator monomer that is a kind of while having peroxy-radical, unsaturated double-bond and polar group through frit reaction extrusion molding.Obtained graft polypropylene has higher polar group grafting rate, moreover it is possible to effectively reduce degradation side reaction common in polypropylene fusion graft process, be conducive to be promoted the mechanical performance of product.This method adapts to the existing technological process of production, can mass production.
Description
Technical field
The present invention relates to a kind of graft polypropylenes more particularly to a kind of polar polypropylene graft and preparation method thereof.
Background technology
Polypropylene (PP) is a kind of highly important general-purpose plastics, has excellent physical property, has been widely used in
Various aspects in the production and living such as building, the energy, chemical industry, communications and transportation.But the low-surface-energy of PP make most of adhesive,
Ink, coating etc. are difficult to adhere on its surface, and nonpolar chemical property also makes it be difficult to and common polar filler (such as glass
Fibre, mineral etc.) it uniformly mixes to further improve intensity.
Graft modification is to improve the common method of PP polarity, wherein squeezed out with free radical initiation grafting, frit reaction again
Method is most commonly seen.There are a large amount of tertiary carbon hydrogen atoms in PP structures, tertiary carbon hydrogen atom is sloughed under the action of peroxide initiator
Form macromolecular radical.But the free radical is unstable, and β-fracture easily occurs and causes molecular chain rupture.Therefore, PP is connecing
Often with serious degradation side reaction while branch is modified, the mechanical strength for eventually leading to product declines.
In existing technical literature, disclose some for PP it is polar-modified, while can reduce again its degradation technology road
Line or method.For example propose that PP and antioxidant are pre- before melting graft reaction in patent CN101724128A, CN101885806A
It is first blended, then enters back into reactive grafting in extruder.Antioxidant plays the role of good capture and quenching free radical, therefore should
Method also counteracts the progress of graft reaction, grafting rate is caused to decline although the molecular chain rupture of PP can be reduced.
Disclosed in the patents such as CN103772612A, CN102321217A, CN1456430A, CN101357968A, CN101942061A
It is the technology path that one or more auxiliary grafted monomers are added in PP grafting process, the auxiliary monomer of introducing includes benzene second
Alkene, oleic acid, acrylate etc. are built containing Dan Shuan or the compound of more double bonds.Although this method can maintain the same of grafting rate
When reduce side reaction, but the auxiliary monomer introduced often has serious penetrating odor (such as styrene, acrylic acid), can not
Meet the operation in actual production and ecological requirements.It proposes on a small quantity repeatedly to add initiator in batches in patent CN104804143A
Enter, by the way that number of free radical is controlled to maintain reaction smooth-going to reduce side reaction, the defects of this method is to operate cumbersome, it is difficult to
Mass can not also avoid the use of styrene completely in addition.Therefore, a kind of simple and easy to do, safety and environmental protection alternative is found
Method produces high grafting rate, the polarity PP grafts of sinking solution become an important subject in industry.
Invention content
For overcome the deficiencies in the prior art, of the invention first purpose is to be to provide a kind of polar polypropylene grafting
Object, it has the characteristics that high grafting rate, low degree of degradation.
Second object of the present invention is to provide for a kind of preparation method of polar polypropylene graft, the preparation method
It can avoid introducing high irritation auxiliary monomer, and overcome the problems, such as that the degradation problem in PP process of grafting and grafting rate are relatively low,
Existing industrialized producing technology flow is adapted to, it can be achieved that continuous production simultaneously.
An object of the present invention adopts the following technical scheme that realization：
A kind of polar polypropylene graft, which is characterized in that including following components by weight：PP resin raw materials
100 parts；0.1-5 parts of initiator monomer；0-2 parts of initiator；0-5 parts of polar monomer；It is grafted 0-5 parts of auxiliary agent；Antioxidant 0.05-1
Part.
Further, the initiator monomer is not only to contain peroxy radicals, but also contain reactive double bond, while have pole
The compound of property functional group.
Further, the initiator monomer is peroxidating Malaysia tert-butyl acrylate.
Further, the addition of the initiator is 0.1-2 parts by weight, and the initiator is peroxide initiator；
The initiator is selected from cumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, dichloro- benzoyl peroxide first
Acyl, the peroxylauric acid tert-butyl ester, 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) hexane, bis- (tert-butyl hydroperoxide isopropyls
Base) benzene, tert butyl isopropyl benzene peroxide, peroxidized t-butyl perbenzoate, one kind in peroxide acetic acid butyl ester or more
Kind.Wherein preferred cumyl peroxide, di-tert-butyl peroxide and 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) oneself
One or more of alkane.
Further, the addition of the polar monomer is 0.1-5 parts by weight, and the polar monomer is contains polar functional
The unsaturated carboxylic acid and its derivative of group；The polar monomer is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, clothing health
Acid, maleic anhydride, 5- norbornane -2,3- dicarboxylic anhydrides, itaconic anhydride, methyl-maleic acid acid anhydride, methyl acrylate, methyl-prop
One or more of e pioic acid methyl ester, ethyl acrylate, ethyl methacrylate.
Further, the addition of the grafting auxiliary agent is 0.1-5 parts by weight, and the grafting auxiliary agent is selected from styrene, right
Methyl styrene, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane tris third
Olefin(e) acid ester, trimethylol-propane trimethacrylate, ethoxylated trimethylolpropane triacrylate, polyether polyol three
In acrylate, triallyl isocyanurate, double pentaerythritol methacrylate and double trimethylolpropane acrylate
It is one or more kinds of.
Further, the antioxidant is selected from dilauryl thiodipropionate, antioxidant 1010, antioxidant 1076, antioxygen
One or more of agent 1330, irgasfos 168, antioxidant 618, antioxidant 215 and antioxidant 225.
Realize that second object of the present invention can reach by adopting the following technical scheme that：
A kind of preparation method of polar polypropylene graft, which is characterized in that including：
Mixing step：The initiator monomer of the PP resin raw materials of formula ratio and formula ratio is uniformly mixed, obtains mixture；
Frit reaction step：Mixture is placed in grafting equipment and carries out frit reaction, the grafting equipment includes mixing
Area, grafting area and terminator, wherein, mixed zone is controlled at 130-200 DEG C, and grafting area is controlled at 150-230 DEG C, eventually
Only area is controlled at 150-220 DEG C；The initiator, polar monomer, grafting auxiliary agent of formula ratio are added in mixed zone, in terminator
The antioxidant of formula ratio is added in, extruding pelletization obtains polar polypropylene graft.
Further, in frit reaction step, the equipment that is grafted is single screw extrusion machine, single screw rod draw ratio 20:1-
40:1, screw diameter 60-120mm, screw speed 150-500rpm；Either, the grafting equipment is double screw extruder, double
Screw slenderness ratio 28:1-40:1, screw diameter 35-75mm, screw speed 150-500rpm.
Further, in frit reaction step, mixed zone is controlled at 150-190 DEG C；Be grafted area controlled at
170-220℃；Terminator is controlled at 170-210 DEG C.
The beneficial effects of the present invention are：
1st, a kind of new reactive component-initiator monomer is introduced in polar polypropylene graft of the invention.Thisization
Closing object both has peroxy radicals, also has unsaturated double-bond, while have polar functional group.After high-temperature fusion causes, mistake
Oxide group, which decomposes, generates the free radical containing polar functional group, be then grafted to obtained on PP macromolecular chains the macromolecular of polarity from
By base.On the other hand, intramolecular crosslinking is formed containing reactive C=C double bonds and macromolecular radical simultaneously on the free radical
So as to resist the interior degradation of PP molecules.Since intramolecular is drawn simultaneously containing initiation group, reactive group and polar group, decomposition
Hair, grafting and cross-linking reaction can occur substantially in same intramolecular, reaction efficiency be effectively increased, so as to obtain higher polarity
Group grafting rate.In addition, the free radical more than needed and reactive functional groups of its generation can also be reacted with other polar monomers, into
One step promotes the polarity of PP grafts.Therefore, polar polypropylene graft of the invention have high grafting rate, low degree of degradation it is excellent
Point.
2nd, preparation method of the invention can avoid introducing high irritation auxiliary monomer, and overcome in PP process of grafting
Degradation problem and the relatively low problem of grafting rate, while existing industrialized producing technology flow is adapted to, it can be achieved that continuous production.The system
Polar polypropylene graft is prepared with higher polar group grafting rate in Preparation Method, moreover it is possible to effectively reduce polypropylene fusion
Common degradation side reaction in grafting process is conducive to be promoted the mechanical performance of product.This method adapts to existing production technology stream
Journey, can mass production.
Specific embodiment
In the following, with reference to specific embodiment, the present invention is described further, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
A kind of polar polypropylene graft, including following components by weight：100 parts of PP resin raw materials；Initiator
0.1-5 parts of monomer；0-2 parts of initiator；0-5 parts of polar monomer；It is grafted 0-5 parts of auxiliary agent；0.05-1 parts of antioxidant.
As the mode that further carries out, the PP resin raw materials are not particularly limited, and can be selected from homopolymerization PP, copolymerization
One or more mixtures in PP, block PP and anti-impact PP；Raw material form, can also either pellet can also be powder
It is the mixture of the two.
As the mode that further carries out, the initiator monomer is not only to contain peroxy radicals, but also contains reactivity
Double bond, while there is the compound of polar functional group.Preferably, peroxidating Malaysia tert-butyl acrylate can be selected.
As mode is further carried out, in order to adjust the mobility of product and Technological adaptability, the polarity PP grafting
The component of object is also comprising initiator, but not necessarily.Preferably, the initiator is peroxide initiator, may be selected from
Aoxidize diisopropylbenzene (DIPB), di-tert-butyl peroxide, benzoyl peroxide, dichloro- benzoyl peroxide, peroxylauric acid uncle
Butyl ester, 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) hexane, bis- (t-butylperoxyisopropyl) benzene, tertiary butyl isopropyl
One or more of phenyl peroxide, peroxidized t-butyl perbenzoate, peroxide acetic acid butyl ester.Wherein preferred mistake
Aoxidize diisopropylbenzene (DIPB), di-tert-butyl peroxide and one kind in 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) hexane or
It is two or more.
As mode is further carried out, in order to save cost and improve the grafting rate of polar group, the polarity PP connects
The component of branch object is also comprising polar monomer, but not necessarily.Preferably, the polar monomer be containing polar functional group not
Saturated carboxylic acid and its derivative may be selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, 5- drops
Bornylane -2,3- dicarboxylic anhydrides, itaconic anhydride, methyl-maleic acid acid anhydride, methyl acrylate, methyl methacrylate, acrylic acid
One or more of ethyl ester, ethyl methacrylate.One kind in wherein preferred acrylic acid, maleic acid, maleic anhydride
It is or two or more.
As mode is further carried out, in order to improve the grafting rate of polar group and adjustment product mobility, the pole
Property PP grafts component also comprising grafting auxiliary agent, but not necessarily.Preferably, the grafting auxiliary agent is selected from styrene, right
Methyl styrene, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane tris third
Olefin(e) acid ester, trimethylol-propane trimethacrylate, ethoxylated trimethylolpropane triacrylate, polyether polyol three
In acrylate, triallyl isocyanurate, double pentaerythritol methacrylate and double trimethylolpropane acrylate
It is one or more kinds of.Wherein in optimization styrene, trimethylolpropane trimethacrylate and Triallyl isocyanurate
It is one or more kinds of.
As further carrying out mode, in order to terminate reaction and improve the storage stability of product, the polarity PP connects
The component of branch object also includes antioxidant.Preferably, the antioxidant be selected from dilauryl thiodipropionate, antioxidant 1010,
One or both of antioxidant 1076, antioxidant 1330, irgasfos 168, antioxidant 618, antioxidant 215 and antioxidant 225
More than.Wherein, preferably one or more of antioxidant 1010, antioxidant 1076, irgasfos 168 and antioxidant 215.
A kind of preparation method of polar polypropylene graft, including：
Mixing step：The initiator monomer of the PP resin raw materials of formula ratio and formula ratio is uniformly mixed, obtains mixture；
Frit reaction step：Mixture is placed in grafting equipment and carries out frit reaction, the grafting equipment includes mixing
Area's (preceding reaction zone), grafting area (main reaction region) and terminator, wherein, mixed zone is controlled at 130-200 DEG C, the control of grafting area
Temperature processed is 150-230 DEG C, and terminator is controlled at 150-220 DEG C；Initiator, the polarity list of formula ratio are added in mixed zone
Body, grafting auxiliary agent, add in the antioxidant of formula ratio, extruding pelletization obtains polar polypropylene graft in terminator.
As the mode that further carries out, in frit reaction step, the grafting equipment is single screw extrusion machine, single screw rod
Draw ratio 20:1-40:1, preferably 30:1-36：1；Screw diameter 60-120mm, preferably 90mm；Screw speed 150-500rpm, it is excellent
Select 200-400rpm.Either, the equipment that is grafted is double screw extruder, twin-screw draw ratio 28:1-40:1, preferably 28:
1-36:1；Screw diameter 35-75mm, preferably 65mm；Screw speed 150-500rpm, preferably 200-400rpm.It is grafted in equipment
It is again preferred using double screw extruder.
As the mode that further carries out, in frit reaction step, mixed zone is controlled at 150-190 DEG C；It is grafted area
Controlled at 170-220 DEG C；Terminator is controlled at 170-210 DEG C.
Specific embodiment of the present invention when following, used raw material, equipment etc. remove special limit in the following embodiments
It can be obtained outside fixed by buying pattern.
Embodiment 1：
A kind of preparation method of polar polypropylene graft, including：
By 100 parts of homopolymerization PP resin raw materials (melt index 11g/10min (230 DEG C, 2.16kg)) and 2.5 parts of peroxidating horses
Carry out acid butyl ester to add in mixing machine, mixing speed 1000r/min mixes 5min.Uniformly mixed material is put into φ 65 couples
In screw extruder, screw slenderness ratio 36:1, three reaction zone temperatures are 190 DEG C, screw speed 300rpm.At extruder end
Only area adds in 0.3 part of antioxidant 215 by weighing balance, and extruding pelletization obtains polarity PP grafts of the present invention.
Embodiment 2：
A kind of preparation method of polar polypropylene graft, including：
By 100 parts of homopolymerization PP resin raw materials (melt index 11g/10min (230 DEG C, 2.16kg)) and 5 parts of peroxidating Malaysias
Acid butyl ester is added in mixing machine, mixing speed 1000r/min, mixes 5min.Uniformly mixed material is put into 65 pairs of spiral shells of φ
In bar extruder, screw slenderness ratio 36:1, three reaction zone temperatures are 190 DEG C, screw speed 300rpm.It is terminated in extruder
Area adds in 0.3 part of antioxidant 215 by weighing balance, and extruding pelletization obtains polarity PP grafts of the present invention.
Embodiment 3：
A kind of preparation method of polar polypropylene graft, including：
By 100 parts of homopolymerization PP resin raw materials (melt index 11g/10min (230 DEG C, 2.16kg)) and 0.2 part of peroxidating horse
Carry out acid butyl ester to add in mixing machine, mixing speed 1000r/min mixes 5min.Uniformly mixed material is put into φ 65 couples
In screw extruder, screw slenderness ratio 32:1, the temperature of mixed zone, grafting area and terminator is respectively 150,190,180 DEG C, spiral shell
Bar rotating speed 300rpm.1.3 parts of maleic anhydrides and 0.3 part of 2,5- dimethyl -2,5- are added in by weighing balance in extruder mixed zone
Two (tert-butyl hydroperoxide) hexanes.0.1 part of antioxidant 215 is added in by weighing balance in extruder terminator, extruding pelletization obtains
Polarity PP grafts of the present invention.
Embodiment 4：
A kind of preparation method of polar polypropylene graft, including：
By 100 parts of copolymerization PP resin raw materials (melt index 3.0g/10min (230 DEG C, 2.16kg)) and 1 part of peroxidating horse
Carry out acid butyl ester to add in mixing machine, mixing speed 1000r/min mixes 5min.Uniformly mixed material is put into φ 65 couples
In screw extruder, screw slenderness ratio 32:1, the temperature of mixed zone, grafting area and terminator is respectively 160,210,200 DEG C, spiral shell
Bar rotating speed 300rpm.2.5 parts of maleic acids are added in by weighing balance in extruder mixed zone.Pass through weighing balance in extruder terminator
0.1 part of irgasfos 168 and 0.1 part of antioxidant 1010, extruding pelletization are added in, obtains polarity PP grafts of the present invention.
Embodiment 5：
A kind of preparation method of polar polypropylene graft, including：
By 100 parts of anti-impact PP resin raw materials (melt index 1.8g/10min (230 DEG C, 2.16kg)) and 5 parts of peroxidating horses
Carry out acid butyl ester to add in mixing machine, mixing speed 1000r/min mixes 5min.Uniformly mixed material is put into φ 65 couples
In screw extruder, screw slenderness ratio 32:1, the temperature of mixed zone, grafting area and terminator is respectively 150,220,190 DEG C, spiral shell
Bar rotating speed 200rpm.0.1 part of cumyl peroxide is added in by weighing balance in extruder mixed zone.Lead in extruder terminator
It crosses weighing balance and adds in 0.2 part of irgasfos 168 and 0.1 part of antioxidant 1010, extruding pelletization, obtain polarity PP grafting of the present invention
Object.
Embodiment 6：
A kind of preparation method of polar polypropylene graft, including：
By 100 parts of homopolymerization PP resin raw materials (melt index 11g/10min (230 DEG C, 2.16kg)) and 2.5 parts of peroxidating horses
Carry out acid butyl ester to add in mixing machine, mixing speed 1000r/min mixes 5min.Uniformly mixed material is put into φ 65 couples
In screw extruder, screw slenderness ratio 36:1, three reaction zone temperatures are 190 DEG C, screw speed 300rpm.It is mixed in extruder
It closes area and 0.5 part of trimethylolpropane trimethacrylate is added in by weighing balance.In extruder terminator 0.5 is added in by weighing balance
Part antioxidant 215, extruding pelletization obtain polarity PP grafts of the present invention.
Embodiment 7：
A kind of preparation method of polar polypropylene graft, including：
By 100 parts of copolymerization PP resin raw materials (melt index 8g/10min (230 DEG C, 2.16kg)) and 0.5 part of peroxidating horse
Carry out acid butyl ester to add in mixing machine, mixing speed 1000r/min mixes 5min.Uniformly mixed material is put into φ 65 couples
In screw extruder, screw slenderness ratio 36:1, the temperature of mixed zone, grafting area and terminator is respectively 150,210,200 DEG C, spiral shell
Bar rotating speed 200rpm.1 part of maleic anhydride, 0.2 part of 2,5- dimethyl -2,5- two are added in by weighing balance in extruder mixed zone
(tert-butyl hydroperoxide) hexane and 0.5 part of styrene.0.05 part of antioxidant 215 is added in by weighing balance in extruder terminator,
Extruding pelletization obtains polarity PP grafts of the present invention.
Comparative example 1：
A kind of preparation method of graft polypropylene, including：
100 parts of homopolymerization PP resin raw materials (melt index 11g/10min (230 DEG C, 2.16kg)) are put into 65 pairs of spiral shells of φ
In bar extruder, screw slenderness ratio 36:1, three reaction zone temperatures are 190 DEG C, screw speed 300rpm.It is mixed in extruder
Area adds in 2.5 parts of maleic acids by weighing balance；0.3 part of antioxidant 215 is added in by weighing balance in extruder terminator, extrusion is made
Grain, obtains comparative example PP grafts.
Comparative example 2：
A kind of preparation method of graft polypropylene, including：
100 parts of anti-impact PP resin raw materials (melt index 1.8g/10min (230 DEG C, 2.16kg)) are put into 65 pairs of spiral shells of φ
In bar extruder, screw slenderness ratio 32:1, the temperature of mixed zone, grafting area and terminator is respectively 150,220,190 DEG C, screw rod
Rotating speed 200rpm.0.1 part of cumyl peroxide is added in by weighing balance in extruder mixed zone.Pass through in extruder terminator
Weighing balance adds in 0.2 part of irgasfos 168 and 0.1 part of antioxidant 1010, extruding pelletization, obtains comparative example PP grafts.
Comparative example 3：
A kind of preparation method of graft polypropylene, including：
100 parts of homopolymerization PP resin raw materials (melt index 11g/10min (230 DEG C, 2.16kg)) are put into 65 pairs of spiral shells of φ
In bar extruder, screw slenderness ratio 32:1, the temperature of mixed zone, grafting area and terminator is respectively 150,190,180 DEG C, screw rod
Rotating speed 300rpm.1.5 parts of maleic anhydrides and 0.3 part of 2,5- dimethyl -2,5- two are added in by weighing balance in extruder mixed zone
(tert-butyl hydroperoxide) hexane.0.1 part of antioxidant 215 is added in by weighing balance in extruder terminator, extruding pelletization obtains pair
Ratio PP grafts.
Comparative example 4：
A kind of preparation method of graft polypropylene, including：
100 parts of copolymerization PP resin raw materials (melt index 8g/10min (230 DEG C, 2.16kg)) are put into 65 twin-screws of φ
In extruder, screw slenderness ratio 36:1, the temperature of mixed zone, grafting area and terminator is respectively 150,210,200 DEG C, and screw rod turns
Fast 200rpm.1.5 parts of maleic anhydrides, 0.2 part of two (uncle of 2,5- dimethyl -2,5- are added in by weighing balance in extruder mixed zone
Butyl peroxy) hexane and 0.5 part of styrene.0.05 part of antioxidant 215 is added in by weighing balance in extruder terminator, is squeezed out
It is granulated, obtains comparative example PP grafts.
The PP graft performance comparisons of 1 each embodiment and comparative example of table
In above-mentioned table 1, its palliating degradation degree before and after being PP graft reactions of melt index change rate reflection.Melt index changes
Rate is bigger, and degradation is more.Its computational methods is as follows：
In above-mentioned table 1, the test method of grafting rate uses acid-base titration.Grafting rate is higher, and the polarity of PP grafts is got over
By force.
As it can be seen from table 1 compared to comparative example 1-4,1-7 of the embodiment of the present invention has relatively low melt index change rate,
Show to degrade less；With higher grafting rate, show that polarity is stronger.
The above embodiment is only the preferred embodiment of the present invention, it is impossible to the scope of protection of the invention is limited with this,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of polar polypropylene graft, which is characterized in that including following components by weight：PP resin raw materials 100
Part；0.1-5 parts of initiator monomer；0-2 parts of initiator；0-5 parts of polar monomer；It is grafted 0-5 parts of auxiliary agent；0.05-1 parts of antioxidant.
2. polar polypropylene graft as described in claim 1, which is characterized in that the initiator monomer is both to contain peroxide
Change group, and contain reactive double bond, while there is the compound of polar functional group.
3. polar polypropylene graft as claimed in claim 2, which is characterized in that the initiator monomer is peroxidating Malaysia
Tert-butyl acrylate.
4. polar polypropylene graft as described in claim 1, which is characterized in that the addition of the initiator is 0.1-2
Parts by weight, the initiator are peroxide initiator；The initiator is selected from cumyl peroxide, di-tert-butyl peroxide
Object, benzoyl peroxide, dichloro- benzoyl peroxide, the peroxylauric acid tert-butyl ester, two (tertiary fourths of 2,5- dimethyl -2,5-
Base peroxidating) hexane, bis- (t-butylperoxyisopropyl) benzene, tert butyl isopropyl benzene peroxide, perbenzoic acid uncle
It is one or more in butyl ester, peroxide acetic acid butyl ester.Wherein preferred cumyl peroxide, di-tert-butyl peroxide and
One or more of 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) hexane.
5. polar polypropylene graft as described in claim 1, which is characterized in that the addition of the polar monomer is 0.1-
5 parts by weight, the polar monomer are unsaturated carboxylic acid and its derivative containing polar functional group；The polar monomer is selected from third
Olefin(e) acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, 5- norbornane -2,3- dicarboxylic anhydrides, itaconic anhydride,
One kind in methyl-maleic acid acid anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate
It is or two or more.
6. polar polypropylene graft as described in claim 1, which is characterized in that the addition of the grafting auxiliary agent is 0.1-
5 parts by weight, the grafting auxiliary agent are selected from styrene, p-methylstyrene, divinylbenzene, ethylene glycol diacrylate, diformazan
Base acrylic acid glycol ester, trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, ethoxylation three
Hydroxymethyl-propane triacrylate, polyether polyol triacrylate, triallyl isocyanurate, six propylene of bipentaerythrite
One or more of acid esters and double trimethylolpropane acrylate.
7. polar polypropylene graft as described in claim 1, which is characterized in that the antioxidant is selected from thio-2 acid two
Lauryl, antioxidant 1010, antioxidant 1076, antioxidant 1330, irgasfos 168, antioxidant 618, antioxidant 215 and antioxidant
One or more of 225.
A kind of 8. preparation method of polar polypropylene graft as described in claim 1-7 any one, which is characterized in that packet
It includes：
Mixing step：The initiator monomer of the PP resin raw materials of formula ratio and formula ratio is uniformly mixed, obtains mixture；
Frit reaction step：Mixture is placed in grafting equipment and carries out frit reaction, the grafting equipment includes mixed zone, connects
Branch area and terminator, wherein, mixed zone is controlled at 130-200 DEG C, and grafting area is controlled at 150-230 DEG C, terminator
Controlled at 150-220 DEG C；The initiator, polar monomer, grafting auxiliary agent of formula ratio are added in mixed zone, is added in terminator
The antioxidant of formula ratio, extruding pelletization obtain polar polypropylene graft.
9. the preparation method of polar polypropylene graft as claimed in claim 8, which is characterized in that in frit reaction step,
The equipment that is grafted is single screw extrusion machine, single screw rod draw ratio 20:1-40:1, screw diameter 60-120mm, screw speed
150-500rpm；Either, the equipment that is grafted is double screw extruder, twin-screw draw ratio 28:1-40:1, screw diameter
35-75mm, screw speed 150-500rpm.
10. the preparation method of polar polypropylene graft as claimed in claim 8, which is characterized in that in frit reaction step,
Mixed zone is controlled at 150-190 DEG C；Area is grafted controlled at 170-220 DEG C；Terminator is controlled at 170-210
℃。
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337016A (en) * | 2018-10-12 | 2019-02-15 | 南京棠城塑胶有限公司 | The technique of crosslinking side reaction is generated in a kind of control process of grafting |
| CN109796912A (en) * | 2018-12-27 | 2019-05-24 | 广州鹿山新材料股份有限公司 | A kind of modified polypropene hot melt adhesive and preparation method thereof |
| CN110872417A (en) * | 2018-08-29 | 2020-03-10 | 国家能源投资集团有限责任公司 | Spinning master batch, polypropylene fiber and preparation method thereof, and polypropylene fiber product |
| CN111440271A (en) * | 2020-04-13 | 2020-07-24 | 广州鹿山新材料股份有限公司 | Maleic anhydride grafted polyolefin wax, hot-melt pressure-sensitive adhesive modified by using same, and preparation method and application of hot-melt pressure-sensitive adhesive |
| CN111978472A (en) * | 2020-08-27 | 2020-11-24 | 哈尔滨理工大学 | Preparation method of silane grafted modified polypropylene by melting method |
| CN114292363A (en) * | 2021-12-16 | 2022-04-08 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN114380951A (en) * | 2021-12-28 | 2022-04-22 | 金发科技股份有限公司 | Polar component grafted polypropylene material and preparation method and application thereof |
| CN117209670A (en) * | 2023-10-19 | 2023-12-12 | 上海泽明塑胶有限公司 | Grafted polypropylene and preparation method thereof |
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| CN101313046A (en) * | 2005-11-25 | 2008-11-26 | 三井化学株式会社 | Sealing material for solar cell, sheet for solar-cell sealing, and solar cell module employing these |
| CN106905491A (en) * | 2017-01-26 | 2017-06-30 | 厦门内加湖新材料科技有限公司 | Polypropylene-base acid modified grafts and the adhesive containing the graft |
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| US4136136A (en) * | 1976-06-14 | 1979-01-23 | The University Of Akron | Graft copolymers of hydrocarbons and small ring heterocyclic compounds and process for the preparation thereof |
| CN101313046A (en) * | 2005-11-25 | 2008-11-26 | 三井化学株式会社 | Sealing material for solar cell, sheet for solar-cell sealing, and solar cell module employing these |
| CN106905491A (en) * | 2017-01-26 | 2017-06-30 | 厦门内加湖新材料科技有限公司 | Polypropylene-base acid modified grafts and the adhesive containing the graft |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110872417A (en) * | 2018-08-29 | 2020-03-10 | 国家能源投资集团有限责任公司 | Spinning master batch, polypropylene fiber and preparation method thereof, and polypropylene fiber product |
| CN109337016A (en) * | 2018-10-12 | 2019-02-15 | 南京棠城塑胶有限公司 | The technique of crosslinking side reaction is generated in a kind of control process of grafting |
| CN109337016B (en) * | 2018-10-12 | 2021-04-06 | 南京棠城塑胶有限公司 | Process for controlling cross-linking side reaction generated in grafting reaction process |
| CN109796912A (en) * | 2018-12-27 | 2019-05-24 | 广州鹿山新材料股份有限公司 | A kind of modified polypropene hot melt adhesive and preparation method thereof |
| CN109796912B (en) * | 2018-12-27 | 2022-03-11 | 广州鹿山新材料股份有限公司 | Modified polypropylene hot melt adhesive and preparation method thereof |
| CN111440271A (en) * | 2020-04-13 | 2020-07-24 | 广州鹿山新材料股份有限公司 | Maleic anhydride grafted polyolefin wax, hot-melt pressure-sensitive adhesive modified by using same, and preparation method and application of hot-melt pressure-sensitive adhesive |
| CN111978472A (en) * | 2020-08-27 | 2020-11-24 | 哈尔滨理工大学 | Preparation method of silane grafted modified polypropylene by melting method |
| CN114292363A (en) * | 2021-12-16 | 2022-04-08 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN114292363B (en) * | 2021-12-16 | 2023-11-24 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN114380951A (en) * | 2021-12-28 | 2022-04-22 | 金发科技股份有限公司 | Polar component grafted polypropylene material and preparation method and application thereof |
| CN114380951B (en) * | 2021-12-28 | 2023-09-26 | 金发科技股份有限公司 | Polar component grafted polypropylene material and preparation method and application thereof |
| CN117209670A (en) * | 2023-10-19 | 2023-12-12 | 上海泽明塑胶有限公司 | Grafted polypropylene and preparation method thereof |
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