CN105504170B - A kind of preparation method of high melt strength, propylene - Google Patents
A kind of preparation method of high melt strength, propylene Download PDFInfo
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- CN105504170B CN105504170B CN201410487327.6A CN201410487327A CN105504170B CN 105504170 B CN105504170 B CN 105504170B CN 201410487327 A CN201410487327 A CN 201410487327A CN 105504170 B CN105504170 B CN 105504170B
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Abstract
The present invention relates to a kind of preparation method of high melt strength, propylene, crosslinking agent antioxidant of this method by polypropylene, branched accelerating agent, Third monomer, 1 minute half life temperature less than 135 DEG C carries out graft reaction by double screw extruder under semi-molten state and obtains.Compared with other melt-mixing methods, pp material carries out being initiated the chemical reaction based on graft reaction under semi-molten semisolid first near fusing point the method for the present invention, advantageously forms long-chain branching polypropylene, while avoiding polyacrylic a large amount of degradations.The method of the present invention is simple for process, is suitable for industrial-scale and manufactures, and the melt strength of acquired high melt strength, propylene is significantly improved compared with plain polypropylene under same melt flow rate, and the degree of cross linking is less than 2%.
Description
Technical field
The present invention relates to a kind of preparation methods of high melt strength, propylene, belong to polypropylene technology field.
Background technology
Polypropylene is one of the thermoplastic macromolecule material of most development prospect.Compared with other general-purpose thermoplastic plastics,
Polypropylene has that density is small, nontoxic, easy processing, mechanical mechanics property are good and raw material sources are wide, lower-price characteristic, extensively
It is general to apply in the fields such as automobile, household electrical appliance, electronics, packaging and building materials and furniture.But it is polymerize with coordination catalysis poly-
Propylene is in mostly line style backbone, shows as partially crystallizable state, softening point is with fusing point very close to when temperature is more than fusing point
Its melt strength declines rapidly afterwards, so as to cause the low disadvantage with Sag Resistance difference of its melt strength.This makes polypropylene exist
When elongational flow, melt cannot show strain hardening effect, be lacked to directly contribute some of polypropylene in melt-processed
Fall into, be included in edge curl and contraction, the sag that occurs in thermoforming and part when high speed extrusion coating it is thinning, in multilayer
Fluid flowing instability and gas is easy to escape, aggregation in foaming process when structure is coextruded, walls bear incessantly gas
Bubble pressure while and lead to rupture of caving in, it is difficult to obtain the foamed plastics of high quality.The presence of these defects, seriously limits polypropylene
Application in fields such as extrusion foaming, thermoforming, extrusion coated and inflation films.
It is the key that improve its hot formability and foam process performance with before to prepare high melt strength, propylene (HMS PP)
It carries, therefore the development of HMS PP causes the extensive concern of domestic and international industrial circle and academia in recent years.The MOLECULE DESIGN of HMSPP
It is mainly reflected in three aspects and improves molecular weight, widen molecular weight distribution and introduce long branched structure.Specific implementation method master
There are blending method, post-reactor method, reactor synthetic method and cross-linking method.
It is to use earliest to select HDPE, LDPE and line polymer blending with certain melt strength or strain hardenability
In one of the method for improving melt strength.As to disclose a kind of high fondant-strength poly- for Chinese patent 200910037289.3
Propylene material and preparation method.High melt strength polypropylene material is by the polypropylene of 100 parts by weight, the high-melting-point of 5-60 parts by weight
Crystalline polymer, the compatilizer of 2-50 parts by weight, the polyethylene of 0-40 parts by weight and other auxiliary agents composition；Preparation method
It is：By polypropylene, high-melting-point crystalline polymer, compatilizer, polyethylene, processing aid measured by formula ratio and uniformly
Then premix carries out melt blending under control temperature, rotating speed by screw extruder and obtains.The blending method of this similar patent,
Feature is simple and convenient and low cost, but the disadvantage is that resin can lose certain performances, such as mechanical property etc. in blending, simultaneously
It also needs to consider the problems of the compatibility between each phase and the therefore performance decline of generation, is not excellent in this way
Choosing method.
Reactive extrursion, which is modified, to be made by screw extruder progress polypropylene with other materials blending reaction fusion-grafting
The polypropylene of standby high fondant-strength.This method due to its economy easy to operate, be suitble to industrialized production and as using at present
One of main method.It connects polypropylene chains or the using chemical free radical initiator in the free base location of propylene polymer backbone
Two monomers, to obtain the acrylic polymers of certain degree of branching.It may relate to initiator, grafted monomers, more in preparation process
Function monomer and Third monomer etc..
100 parts by weight of polypropylene and 0.1-10 parts by weight propylene esters of gallic acid are total to by Chinese patent ZL 200810050434.7
Polycondensation monomer, the reversible stabilizer of 0.001-5 parts by weight free radicals and 0.001-2 parts by weight radical initiator are at 170-230 DEG C
Frit reaction squeezes out to obtain high melt strength, propylene.It is strong that Chinese patent ZL 200610113313.3 discloses a kind of high melt
Preparation method is spent, the raw material reactive extrursion of polypropylene, double bond containing monomer, peroxide and thiurams monomer will be included
It obtains.Chinese patent ZL 200610017181.4 discloses a kind of high melt strength, propylene and preparation method thereof, by 70-
Three kinds of components of acrylic ester compound of 99.8% polypropylene, the vinyl polybutadiene of 0.1-29.9%, 0.1-25%
After mixing, the progress reactive extrursion at 190-240 DEG C is added in extruder to obtain.Chinese patent
ZL200810051243.2 by by polypropylene, the monomer containing double bond, peroxide, dithiocarbamates substance,
Antioxidant obtains high melt strength, propylene in 180-260 DEG C of melt blending.Chinese patent 200810061200.2 provides one
Kind of high melt strength, propylene, by weight calculate 100 parts of acrylic resins, 0.01-10 parts of peroxide, 1-10 parts it is multifunctional
Single group body, 0.01-8 parts of branched accelerating agents and 0.1-2 portions of nucleating agents squeeze out to obtain by double screw extruder.Chinese patent
200810203843.6 providing a kind of preparation method of long-chain branch high fused mass strength polypropylene resin, include the following steps：It will
After polypropylene, initiator, styrene monomer, polyfunctional monomer and calcium stearate mixing, 170-210 DEG C of double screw extruder is added
Melting extrusion obtains.Chinese patent 201010107870.0 discloses a kind of preparation method of high melt strength, propylene, will
100 parts by weight of polypropylene, 0.5-5 parts by weight alkadienes, 0.01-10 parts by weight acrylate and 0.01-3 parts by weight initiation
Agent, the frit reaction at 150-250 DEG C and obtain.These prepare long chain branching or grafting poly- third using pyroreaction extrusion method
Alkene is frequently accompanied by serious degradation of polypropylene process, the melt flow rate (MFR) reproducibility of obtained long-chain branching polypropylene
It is very poor.In addition, using above-mentioned patent the method, because degradation of polypropylene makes molecular weight of product narrow distribution in reaction process,
It is still limited to improving polyacrylic melt strength although introducing long-chain branch by grafting.
Chinese patent 200810224863.1 disclose it is a kind of in the copolymer polypropylene powder of ethylene contents >=10% plus
Enter 2,5 dimethyl 2,5 bis hexane or 1,3- di-t-butyls cumene improves poly- third through melting extrusion
The method of alkene melt strength.This method can only be directed to the very high polypropylene of ethylene copolymer amount, and the scope of application is very narrow.
Invention content
The main object of the present invention is to solve the deficiencies in the prior art, provides a kind of preparation side of high melt strength, propylene
Method, can significantly improve polyacrylic melt strength height and the degree of cross linking is low, particularly suitable for industrialized production.
Technical solution
A kind of preparation method of high melt strength, propylene, comprises the steps of：
(1) by 0.5~5 part of branched accelerating agent, 1.0~4.0 parts of Third monomer, 0.5~1.25 part of crosslinking agent and
0.3~0.6 part of antioxidant, which is added in 3~5 parts of acetone, is sufficiently stirred dispersion, obtains auxiliary agent mixed liquor；
(2) under an inert atmosphere, 100 parts of polypropylene powders are uniformly mixed with above-mentioned auxiliary agent mixed liquor, as mixture；
(3) it adds mixture into parallel dual-screw extruding machine, carries out melting extrusion, while extracting small molecule volatilization
Object, extrudate through cooling granulation to get；
The polypropylene powder is the ecosystem polypropylene powder for being not added with any auxiliary agent, selected from homopolypropylene or altogether
Poly- polypropylene.Wherein, the homopolypropylene melt flow rate (MFR) is 0.2~20g/10min；The copolymer polypropylene is total to
Polycondensation monomer is one or more in ethylene, 1- butylene, 1- hexenes and 1- octenes, and the content of comonomer is no more than 15wt%.
The draw ratio (L/D) of the parallel dual-screw extruding machine is 46~56.
The extrusion temperature of the parallel dual-screw extruding machine is 160 DEG C~240 DEG C, and material is in double screw extruder
Residence time is between 90~300s.In numerous reaction conditions that polypropylene chemical is modified, temperature is a vital ginseng
Number, various reactions have reaction temperature different susceptibilitys.Usually between 80 DEG C -150 DEG C, monomer is anti-to polyacrylic grafting
It should be easier to occur；And when temperature is easy to happen grafting and cross-linking reaction when between 150-180 DEG C；When temperature is higher than 180 DEG C
When, degradation reaction is occupied an leading position.So post-reactor method should be specifically noted that the selection of reaction condition when synthesizing HMSPP, to the greatest extent may be used
Avoid polyacrylic crosslinking and degradation to energy.
The branched accelerating agent is selected from triallyl cyanurate (TAC), iso-cyanuric acid triallyl ester
(TAIC), trimethylol-propane trimethacrylate (TMPTMA), N, mono- meta-phenylene bismaleimides of N (PDM) or three
The composition of one or more kinds of arbitrary proportions of polysulfide cyanic acid (TCY).
The Third monomer appointing in styrene, divinylbenzene, α-methylstyrene or vinyl ethylo benzene
Meaning is a kind of, optimization styrene.
The crosslinking agent refers to that 1 minute half life temperature is less than 135 DEG C of organic peroxide, is selected from benzoyl peroxide first
Acyl, diacetyl peroxide, dipropyonyl peroxide, diisobutyryl peroxide, dioctanoyl peroxide, dilauroyl peroxide, it is bis- (3,
5,5- trimethyl acetyls) peroxide, benzoyl peroxide, 2,4- dichlorobenzoperoxides, tert-butyl hydroperoxide pivalic acid
The one or more of benzoyl between ester, dioctanoyl peroxide, succinic acid peroxide ester, t-butyl peroxy-isobutylate, peroxidating
The mixture of arbitrary proportion.One or both of benzoyl preferably between benzoyl peroxide, diacetyl peroxide, peroxidating
The mixture of any of the above ratio.
The antioxidant is made of primary antioxidant and auxiliary anti-oxidant, wherein
Primary antioxidant be selected from 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) -1,3,5- triazines -2,4,6 [1H, 3H,
5H] triketone, β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) propionic acid n-octadecyl alcohol esters or four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] any one in pentaerythritol ester, preferably 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) -1,3,
5- triazines -2,4,6 [1H, 3H, 5H] triketone；Auxiliary anti-oxidant is selected from (2,4- di-tert-butyl-phenyls) tris phosphite or pentaerythrite
Any one in bis-phosphite two (2,4- di-tert-butyls phenyl) ester.
Preferably, the weight ratio of primary antioxidant and auxiliary anti-oxidant is 1:1~1:2.
Using the high polyacrylic manufacturing method of melt provided by the present invention, compared with other melt-mixing methods, poly- third
Alkene raw material carries out being initiated the chemical reaction based on graft reaction under semi-molten semisolid first near fusing point, is conducive to shape
At long-chain branching polypropylene, while avoiding polyacrylic a large amount of degradations.The method and process of the present invention is simple, and it is big to be suitable for industry
The melt strength of scale manufacturing, acquired high melt strength, propylene has obviously compared with plain polypropylene under same melt flow rate
It improves, and the degree of cross linking is less than 2%.
Specific implementation mode
Illustrate the present invention in further detail with reference to embodiments, but the present invention is not limited to these Examples.
Explanation：(1) melt flow rate (MFR) (MFR) measures reference standard GB/T 3682-2008 and carries out, determination condition 230
DEG C, 2.16 kilograms of loads；Melt strength is measured in high FordRT2000 types capillary rheometer and matingIt is carried out on 71.97 melt strength analyzers of Rheotens.The a diameter of 9.5mm of rheometer barrel, capillary die
Draw ratio is 30mm/1mm.By sample be placed in 190 DEG C melting 4 minutes after, piston with 0.2mm/s speed squeeze out, code test
Temperature is 190 DEG C.Material strip will be squeezed out to draw into one group of acceleration roll gap at 100mm below die orifice, roll gap 0.2mm adds
Speed is 1.2mm/s2.By instrument institute band software records initial velocity speed, tensile speed and melt tension.Melt strength is disconnected for material strip
Stable tension (cN) before splitting.
(2) test of the degree of cross linking is with reference to following methods：Precise 0.3g or so sample is wrapped with 200 mesh copper mesh, is put into
It flows back 8 hours to being added in the dimethylbenzene boiling solvent of 1% antioxidant 1010, sample taking-up is then placed on vacuum drying oven
In, it dries to constant weight, is cooled to room temperature at 80 DEG C, take out and weigh.Gel content accounts for initial mass according to not compatibilized polypropylene
Percentage calculation：
The degree of cross linking=100 [M0-(M2-M1)]/M0(%)
M in formula0For sample proper mass (g)；M1For the quality of sample after extracting and copper mesh；M2For sample before extracting and copper mesh
Quality (g).
For the ease of statement, what the number in following all examples referred to is all parts by weight.
The screw arrangement of double screw extruder used in following embodiment is：
NISE30/60/1(B)+SE45/60/2+SE30/120/2+SE30/120/2+SE30/120/2+SE30/120/2+
SE30/120/2+SE30/120/2+SE30/120/2+SE30/60/2+KB2/15/2/30°+SE30/120/2+KB2/15/2/
60°+SE30/120/2+KB2/15/2/60°+SE30/60/2+SE45/60/2+SE30/120/2+SP2/15。
Wherein NISE30/60/1 (B) indicates the reversed delivery element of non-engagement of helical pitch 30mm, length 60mm, single head.SE tables
Show that engagement type screwing element, KB indicate that engagement type kneading block, SP indicate axial transitions element, as SE45/60/2 expressions are led
Journey is 45mm, the engagement type screwing element of axial length 60mm, double end；KB2/15/2/30 ° indicates two sections of axial length difference
For 7.5mm, total axial length be 15mm, it is double between, the kneading block that stagger arrangement angle is 30 °；SP2/15 indicates two sections of axial lengths
Respectively 7.5mm, the axial transitions element that total axial length is 15mm；The meaning of remaining symbol is analogized.
Embodiment 1
Double screw extruder used in the present embodiment is screw diameter 30mm, the Co rotating Twin Screw Extrusion that draw ratio is 52
Machine.
By 3 parts of styrene, 1.25 parts of benzoyl peroxide, 0.5 part of triallyl cyanurate, 0.2 part of β-(4-
Hydroxyl -3,5- di-tert-butyl-phenyls) propionic acid n-octadecyl alcohol ester, 0.4 part of (2,4- di-tert-butyl-phenyls) tris phosphite be added
To being thoroughly mixed in 3 parts of acetone, auxiliary agent mixed liquor is obtained.By the homopolymerization that 100 parts of melt flow rate (MFR)s are 0.2g/10min
Polypropylene powder is added in moderate-speed mixers, and in the presence of inert gas, above-mentioned mixed liquor is sprayed on polypropylene several times
The surface of powder is finally used as mixture after sufficiently mixing.
Above-mentioned mixture is added in double screw extruder and carries out extruding pelletization.The extrusion temperature of double screw extruder is
210℃.Engine speed 80rpm, charging rate 6.0rpm, suction -0.4kg when extrusion.
Obtained high melt strength, propylene is after water-bath cooling pelletizing, after vacuum drying oven is dried 3 hours at 80 DEG C
Carry out properties test.Measured melt flow rate (MFR) is 2.0g/10min, melt strength 28cN, and the degree of cross linking is
0.6%.The melt strength of the plain polypropylene of same melt flow rate is 6cN.
Embodiment 2
Double screw extruder used in the present embodiment is screw diameter 30mm, the Co rotating Twin Screw Extrusion that draw ratio is 46
Machine.
Remaining is substantially the same manner as Example 1, but polypropylene is changed to the homopolypropylene that melt flow rate (MFR) is 2g/10min,
The extrusion temperature of double screw extruder is changed to 190 DEG C.
Auxiliary formula is changed to：
The melt flow rate (MFR) of obtained high melt strength, propylene is 3.6g/10min, melt strength 23cN, is handed over
Connection degree is 0.5%.The melt strength of the plain polypropylene of same melt flow rate is 3.5cN.
Embodiment 3
Double screw extruder used in the present embodiment is screw diameter 30mm, the Co rotating Twin Screw Extrusion that draw ratio is 56
Machine.
Remaining is substantially the same manner as Example 1, but polypropylene is changed to ethylene copolymer amount 10%, melt flow rate (MFR) 10g/
The extrusion temperature of the copolymer polypropylene of 10min, double screw extruder is changed to 180 DEG C.
Auxiliary formula is changed to：
The melt flow rate (MFR) of obtained high melt strength, propylene be 8.4g/10min, melt strength 13.7cN,
The degree of cross linking is 0.3%.The melt strength of the plain polypropylene of same melt flow rate is 0.95cN.
Embodiment 4
Double screw extruder used in the present embodiment is screw diameter 30mm, the Co rotating Twin Screw Extrusion that draw ratio is 48
Machine.
Remaining is substantially the same manner as Example 1, but polypropylene is changed to butene-1 copolymerization amount 4.5%, and melt flow rate (MFR) is
The extrusion temperature of the copolymer polypropylene of 20g/10min, double screw extruder is changed to 220 DEG C.
Auxiliary formula is changed to：
The melt flow rate (MFR) of obtained high melt strength, propylene is 16g/10min, melt strength 9.2cN, is handed over
Connection degree is 1.9%.The melt strength of the plain polypropylene of same melt flow rate is 0.96cN.
Claims (7)
1. a kind of preparation method of high melt strength, propylene, which is characterized in that comprise the steps of：
(1) by 0.5~5 part of branched accelerating agent, 1.0~4.0 parts of Third monomer, 0.5~1.25 part of crosslinking agent and 0.3~
0.6 part of antioxidant, which is added in 3~5 parts of acetone, is sufficiently stirred dispersion, obtains auxiliary agent mixed liquor；
(2) under an inert atmosphere, 100 parts of polypropylene powders are uniformly mixed with above-mentioned auxiliary agent mixed liquor, as mixture；
(3) it adds mixture into parallel dual-screw extruding machine, carries out melting extrusion, while extracting small molecule volatile matter, squeeze
Go out object through cooling granulation to get；
The polypropylene powder is the ecosystem polypropylene powder for being not added with any auxiliary agent, poly- selected from homopolypropylene or copolymerization
Propylene, wherein the homopolypropylene melt flow rate (MFR) is 0.2~20g/10min；The copolymerization list of the copolymer polypropylene
Body is one or more in ethylene, 1- butylene, 1- hexenes and 1- octenes, and the content of comonomer is no more than 15wt%；
The branched accelerating agent is selected from triallyl cyanurate, iso-cyanuric acid triallyl ester or N, mono- metaphenylenes of N
The mixture of one or more of bismaleimide arbitrary proportion；
Any one of the Third monomer in styrene, divinylbenzene, α-methylstyrene or vinyl ethylo benzene；
The crosslinking agent is selected from benzoyl peroxide, diacetyl peroxide, dipropyonyl peroxide, diisobutyryl peroxide, peroxide
Change two decoyls, dilauroyl peroxide, bis- (3,5,5- trimethyl acetyls) peroxide, benzoyl peroxide, 2,4- dichloro mistakes
Benzoyl Oxide, tert-butyl hydroperoxide pivalate, dioctanoyl peroxide, succinic acid peroxide ester, t-butyl peroxy-isobutylate or
The mixture of one or more kinds of arbitrary proportions of benzoyl between peroxidating.
2. the preparation method of high melt strength, propylene as described in claim 1, which is characterized in that the parallel dual-screw
The draw ratio (L/D) of extruder is 46~56.
3. the preparation method of high melt strength, propylene as described in claim 1, which is characterized in that the parallel dual-screw
The extrusion temperature of extruder is 160 DEG C~240 DEG C.
4. the preparation method of high melt strength, propylene as described in claim 1, which is characterized in that the Third monomer is benzene
Ethylene.
5. the preparation method of high melt strength, propylene as described in claim 1, which is characterized in that the crosslinking agent is peroxide
The mixture of one or more of benzoyl arbitrary proportion between change benzoyl, diacetyl peroxide or peroxidating.
6. such as the preparation method of high melt strength, propylene described in any one of claim 1 to 5, which is characterized in that described anti-
Oxygen agent is made of primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is selected from 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) -1,
3,5- triazines -2,4,6 [1H, 3H, 5H] triketone, β-(4- hydroxyl -3,5- di-tert-butyl-phenyls) propionic acid n-octadecyl alcohol ester or four
Any one in [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester；Auxiliary anti-oxidant is selected from (bis- uncles of 2,4-
Butyl phenyl) any one in tris phosphite or pentaerythritol bis-phosphite two (2,4- di-tert-butyls phenyl) ester.
7. the preparation method of high melt strength, propylene as claimed in claim 6, which is characterized in that the primary antioxidant and auxiliary
The weight ratio of antioxidant is 1:1~1:2.
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| CN108570187B (en) * | 2018-05-08 | 2021-06-18 | 广州科莱瑞迪医疗器材股份有限公司 | Polypropylene plate for artificial limb orthopedic appliance and preparation method thereof |
| CN109553723A (en) * | 2018-10-26 | 2019-04-02 | 中国石油化工股份有限公司 | The preparation method of maleic anhydride grafted polymer |
| CN109553724A (en) * | 2018-11-28 | 2019-04-02 | 山东玉皇化工有限公司 | A kind of high melt strength polypropylene material and preparation method thereof |
| CN110154472B (en) * | 2019-05-15 | 2021-06-15 | 江阴中达软塑新材料股份有限公司 | Cigarette film with uniform thickness |
| CN111019164B (en) * | 2019-12-18 | 2022-07-12 | 万华化学集团股份有限公司 | Method for testing proper crosslinking degree of molten polymer |
| CN113896835A (en) * | 2021-10-27 | 2022-01-07 | 中国石油化工股份有限公司 | High-melt-strength polypropylene and preparation method and application thereof |
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| JP3832658B2 (en) * | 2002-06-17 | 2006-10-11 | 株式会社プライムポリマー | Polypropylene resin composition |
| CN101418064B (en) * | 2008-12-02 | 2010-09-15 | 华东理工大学 | Method for preparing long-chain branch high fused mass strength polypropylene resin |
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