CN105777995B - Preparation method of polar polypropylene - Google Patents
Preparation method of polar polypropylene Download PDFInfo
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- CN105777995B CN105777995B CN201410810634.3A CN201410810634A CN105777995B CN 105777995 B CN105777995 B CN 105777995B CN 201410810634 A CN201410810634 A CN 201410810634A CN 105777995 B CN105777995 B CN 105777995B
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 63
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 63
- -1 polypropylene Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 50
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 230000035484 reaction time Effects 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 3
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 2
- 238000006011 modification reaction Methods 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000008961 swelling Effects 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000005457 ice water Substances 0.000 description 12
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 8
- 229920005629 polypropylene homopolymer Polymers 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses polar polypropylene prepared by graft modification by using supercritical propylene as a swelling agent. The preparation method of the product comprises the following steps: placing polypropylene, an initiator and a grafting monomer in a reaction kettle, introducing propylene, heating and pressurizing to a propylene supercritical state, and reacting to obtain a polar polypropylene product. The polar polypropylene product prepared by the method has high grafting rate and small addition amount as a compatilizer.
Description
Technical field
The present invention relates to polar polypropylene prepared by a kind of solid phase graft-modification, more particularly to utilizing supercritical propylene
The polar polypropylene prepared as sweller.
Background technology
Polar polypropylene is with its excellent hydrophily, dyeability, antistatic property, caking property and printing, as compatilizer
With it is polypropene blended compound, be widely used in the fields such as packaging, automobile, advertisement.The method for preparing polar polypropylene is exactly poly-
Polar group is introduced on propylene skeleton, wherein it is most simple and practicable to carry out graft modification to it with the monomer containing polar group
, it receives significant attention.The height of polar polypropylene grafting rate directly determines its additive amount as compatilizer.Therefore, it makes
The polar polypropylene of standby high grafting rate, reduces its additive amount as compatilizer, is the technical problem to be solved in the present invention.
The method that generally use is modified to polypropylene has solid phase grafting, solution graft copolymerization, fusion-grafting and radiation grafting
Deng.In these methods, overcritical material assistance solid phase grafting with its uniqueness the advantages of and receive favor.This is because polypropylene passes through
After crossing overcritical substance processing, backbone structure will not occur significantly to change, and still maintain original good physical chemistry
Matter；Secondly, overcritical material assistance graft polypropylene overcomes some shortcomings existing for traditional handicraft, such as solution
Grafting organic solvent it is a large amount of using and removed it from product, polyacrylic serious chain rupture, solid phase connect in fusion-grafting
Branch be only limitted to surface grafting, be grafted uneven and grafting rate it is low and uncontrollable etc..
The present invention prepares polar polypropylene using supercritical propylene and also has the following advantages that：(1) polypropylene is overcritical third
The swelling effect of alkene is better than other overcritical substances, therefore the polar polypropylene grafting rate prepared is higher；(2) propylene is in polypropylene
It can participate in reacting in graft reaction, improve the grafting efficiency of product, therefore effect is better than other kinds of sweller；(3) surpass
The proper temperature graft modification reaction of critical propylene state carries out, therefore reaction process constant temperature, without adjustment.
At present, the polypropylene of supercritical carbon dioxide graft modification is used in document, application No. is 2011101916469 more
It discloses using supercritical CO2The method for carrying out swelling assistance solid phase graft-modification to polypropylene as sweller and carrying agent,
Swelling and grafting are carried out respectively.And CN101143946 discloses the side of extruding and preparing maleation polypropylene by supercritical reaction
Method.US5663237 is disclosed is put into raw material, monomer and initiator in autoclave simultaneously, is then injected into carbon dioxide simultaneously
It is heated to the reaction process being grafted after supercriticality, reaction pressure 7-20MPa, 50-90 DEG C of reaction temperature.
US5663237A discloses a kind of method of the graft copolymerization in supercritical medium, specially：The critical flow of use
Body can be propylene, and the critical-temperature of propylene is 91.9 DEG C, critical pressure 45.6atm, the process packet of overcritical graft copolymerization
It includes：It adds a polymer in high-pressure reactor, monomer is added to reactor, add in radical polymerization initiator to cause it
The polymer of preceding formation；Enough supercritical solvents are added in, are dissolved at least partly during super critical condition with being realized in reactor
Polymer and monomer；Reactor is heated and is pressurizeed, to realize super critical condition, is kept for the time for being sufficient for graft copolymerization.
Polymer can be polypropylene, and grafted monomers are acrylonitrile, methyl methacrylate, maleic anhydride, methacrylic acid.
US5663237A does not provide reaction temperature and condition and on this condition required of the suitable propylene as supercritical solvent
Grafting time, for different grafting solvents, take different reaction temperature and condition；In overcritical graft reaction, instead
Step is answered to be divided into overcritical swelling and polarity is grafted two steps, the swelling temperature and pressure that this patent utilizes propylene suitable, it will
Two steps of swelling and grafting merge, i.e., complete carrying out Graft Method after graft reaction rather than decompression before pressure release,
US5663237 A do not provide clear description but.
Invention content
Swelling assistance solid phase is carried out to polypropylene as sweller using supercritical propylene it is an object of the present invention to provide a kind of
Graft modification prepares polar polypropylene, overcome reaction pressure height of the existing technology, solvent recovery, pollution environment, grafting it is low,
And graft product is degraded the shortcomings of serious.
The method of the present invention includes the following steps：
Polypropylene, initiator and grafted monomers are added in a kettle, after being passed through propylene, through molten in supercritical propylene
Slow release cooling, obtains polar polypropylene product after swollen, graft reaction.
Term " supercritical propylene " refers to that the pressure of propylene is more than 4.4MPa, and temperature is 90 DEG C or more.
Described grafted monomers are acrylic acid (AA), butyl acrylate (BA), maleic anhydride (MAH), methacrylic acid fourth
Ester (BMA), methyl methacrylate (MMA), methacrylic acid (MAA), styrene (St), ethyl acrylate (EA) and season penta 4
The mixing of one or more of three glycerol acrylate of alcohol (PETA), dosage are the 20%-30% of polypropylene quality.
Described initiator such as conventional azo or per-compound class initiator, can be azodiisobutyronitrile, mistake
Benzoyl Oxide and dicumyl peroxide, dosage are the 2-9% of polypropylene quality.
Graft reaction temperature is 91-115 DEG C, reaction pressure 4.5-7.0MPa, and the reaction time is 0.1-10 hours.
Under the conditions described above, the polar polypropylene properties of product obtained are obviously improved, and grafting rate exists
More than 10%, and maintain the original excellent mechanical property of polypropylene.It can be seen that this product is in grafting process less degradation,
Grafting rate is high, has the bright prospects of industrialized production.
Specific embodiment
The application of the present invention is described further, but embodiment is not intended to limit the protection of the present invention below by embodiment
Range.
Case study on implementation 1
Take the homopolypropylene that 100g melt flow rate (MFR)s are 3g/10min, initiator BPO, DCP and AIBN, quality point
Not Wei 2g, 3g and 2g, grafted monomers selection AA, BA and MAH, quality is respectively 4g, 6g and 15g, is placed in autoclave, is put into pre-
If in the constant temperature oil bath of good temperature, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to finger with high-pressure pump
Constant-pressure.Reaction temperature control is 108 DEG C, reaction pressure 4.6MPa, reaction time 3.6h.After reaction, by high pressure
Kettle takes out, and is cooled down with ice water, slow release.Sample cleanup is taken out, dry, it is 11.8% to calculate polar polypropylene grafting rate.
Case study on implementation 2：
Take the homopolypropylene that 100g melt flow rate (MFR)s are 5g/10min, initiator AIBN, quality 6g, grafting list
Body selects AA, MAH, BMA and St, and quality is respectively 10g, 8g, 6g and 2g, is placed in autoclave, is put into the perseverance for presetting temperature
In warm oil bath, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to specified pressure with high-pressure pump.Reaction temperature
Degree control is 112 DEG C, reaction pressure 4.6MPa, reaction time 4.7h.After reaction, autoclave is taken out, uses ice water
Cooling, slow release.Sample cleanup is taken out, dry, it is 12.4% to calculate polar polypropylene grafting rate.
Case study on implementation 3
Take the homopolypropylene that 100g melt flow rate (MFR)s are 10g/10min, initiator BPO, quality 7g, grafting list
Body selects MAA, St, EA and PETA, and quality is respectively 7g, 12g, 5g and 4g, is placed in autoclave, is put into the perseverance for presetting temperature
In warm oil bath, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to specified pressure with high-pressure pump.Reaction temperature
Degree control is 120 DEG C, reaction pressure 4.8MPa, reaction time 5.1h.After reaction, autoclave is taken out, uses ice water
Cooling, slow release.Sample cleanup is taken out, dry, it is 12.9% to calculate polar polypropylene grafting rate.
Case study on implementation 4
Take the homopolypropylene that 100g melt flow rate (MFR)s are 15g/10min, initiator DCP, quality 5g, grafting list
Body selects MAA, St, MMA and EA, and quality is respectively 5g, 7g, 9g and 7g, is placed in autoclave, is put into the constant temperature for presetting temperature
In oil bath, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to specified pressure with high-pressure pump.Reaction temperature
Control is 128 DEG C, reaction pressure 4.8MPa, reaction time 6.2h.After reaction, autoclave is taken out, it is cold with ice water
But, slow release.Sample cleanup is taken out, dry, it is 13.7% to calculate polar polypropylene grafting rate.
Case study on implementation 5
The homopolypropylene that 100g melt flow rate (MFR)s are 20g/10min is taken, initiator is BPO and DCP, and quality is respectively
3g and 1g, grafted monomers selection BMA, MAA, MMA and EA, quality is respectively 4g, 6g, 6g and 8g, is placed in autoclave, is put into pre-
If in the constant temperature oil bath of good temperature, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to finger with high-pressure pump
Constant-pressure.Reaction temperature control is 100 DEG C, reaction pressure 5.0MPa, reaction time 6.9h.After reaction, by high pressure
Kettle takes out, and is cooled down with ice water, slow release.Sample cleanup is taken out, dry, it is 10.5% to calculate polar polypropylene grafting rate.
Case study on implementation 6
Take 100g melt flow rate (MFR)s be 18g/10min Propylene polymerization polypropylene, initiator be DCP and AIBN, quality
Respectively 4g and 2g, grafted monomers selection AA, BA, BMA and EA, quality is respectively 2g, 10g, 10g and 2g, is placed in autoclave,
It is put into the constant temperature oil bath for presetting temperature, is first filled with propylene and replaces the air in kettle totally, then inject third with high-pressure pump
Alkene is to specified pressure.Reaction temperature control is 99 DEG C, reaction pressure 5.0MPa, reaction time 7.8h.After reaction, will
Autoclave takes out, and is cooled down with ice water, slow release.Sample cleanup is taken out, dry, calculating polar polypropylene grafting rate is
11.6%.
Case study on implementation 7
Take 100g melt flow rate (MFR)s be 15g/10min Propylene polymerization polypropylene, initiator be BPO and AIBN, quality
Respectively 2g and 5g, grafted monomers selection AA and BA, quality is respectively 12g and 11g, is placed in autoclave, is put into and presets temperature
In the constant temperature oil bath of degree, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to specified pressure with high-pressure pump.
Reaction temperature control is 130 DEG C, reaction pressure 6.0MPa, reaction time 8.3h.After reaction, autoclave is taken out,
It is cooled down with ice water, slow release.Sample cleanup is taken out, dry, it is 13.2% to calculate polar polypropylene grafting rate.
Case study on implementation 8
Take 100g melt flow rate (MFR)s be 12g/10min Propylene polymerization polypropylene, initiator be AIBN and DCP, quality
Respectively 3g and 5g, grafted monomers selection BA, St and PETA, quality is respectively 9g, 9g and 9g, is placed in autoclave, is put into pre-
If in the constant temperature oil bath of good temperature, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to finger with high-pressure pump
Constant-pressure.Reaction temperature control is 92 DEG C, reaction pressure 6.5MPa, reaction time 2.8h.After reaction, by autoclave
It takes out, is cooled down with ice water, slow release.Sample cleanup is taken out, dry, it is 10.1% to calculate polar polypropylene grafting rate.
Case study on implementation 9
Take the Propylene polymerization polypropylene that 100g melt flow rate (MFR)s are 8g/10min, initiator BPO and DCP, quality point
Not Wei 2g and 5g, grafted monomers selection AA, MMA and EA, quality is respectively 7g, 11g and 15g, is placed in autoclave, is put into default
In the constant temperature oil bath of good temperature, be first filled with propylene the air in kettle is replaced it is clean, then with high-pressure pump injection propylene to specifying
Pressure.Reaction temperature control is 122 DEG C, reaction pressure 6.5MPa, reaction time 9.2h.After reaction, by autoclave
It takes out, is cooled down with ice water, slow release.Sample cleanup is taken out, dry, it is 13.9% to calculate polar polypropylene grafting rate.
Case study on implementation 10
The Propylene polymerization polypropylene that 100g melt flow rate (MFR)s are 5g/10min is taken, initiator is BPO and AIBN, and quality is divided
Not Wei 3g and 4g, grafted monomers selection AA, MAH, MAA, MMA and EA, quality is respectively 2g, 4g, 6g, 8g and 10g, is placed in high pressure
It in kettle, is put into the constant temperature oil bath for presetting temperature, is first filled with propylene and replaces the air in kettle totally, then noted with high-pressure pump
Enter propylene to specified pressure.Reaction temperature control is 117 DEG C, reaction pressure 7.0MPa, reaction time 5.6h.Reaction terminates
Afterwards, autoclave is taken out, is cooled down with ice water, slow release.Sample cleanup is taken out, dry, calculating polar polypropylene grafting rate is
14.3%.
Can be seen that the polar polypropylene grafting rate that supercritical propylene is used to prepare by the embodiment 1-10 of table 1 can be with
Reach more than 6%, product has very high polarity, obtains good effect.
Table 1
Compare case study on implementation 1
Take the homopolypropylene that 100g melt flow rate (MFR)s are 3g/10min, initiator BPO, DCP and AIBN, quality point
Not Wei 2g, 3g and 2g, grafted monomers selection AA, BA and MAH, quality is respectively 4g, 6g and 15g, is placed in autoclave, is put into pre-
If in the constant temperature oil bath of good temperature, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to finger with high-pressure pump
Constant-pressure.After swelling, autoclave is taken for 108 DEG C, reaction pressure 4.6MPa, swelling time 1h for reaction temperature control
Go out, cooled down with ice water, slow release.Graft reaction is carried out, for 108 DEG C, reaction pressure is normal pressure for reaction temperature control, during reaction
Between be 2.6h.Sample cleanup is taken out, dry, it is 3.8% to calculate polar polypropylene grafting rate.
Compare case study on implementation 2：
Take the homopolypropylene that 100g melt flow rate (MFR)s are 5g/10min, initiator AIBN, quality 6g, grafting list
Body selects AA, MAH, BMA and St, and quality is respectively 10g, 8g, 6g and 2g, is placed in autoclave, is put into the perseverance for presetting temperature
In warm oil bath, first it is filled with propylene and replaces the air in kettle totally, then inject propylene to specified pressure with high-pressure pump.Reaction temperature
After swelling, autoclave is taken out for 112 DEG C, reaction pressure 4.6MPa, swelling time 1.5h for degree control, cold with ice water
But, slow release.Graft reaction is carried out, reaction temperature control is 112 DEG C, and reaction pressure is normal pressure, reaction time 2.2h.It takes
Go out sample cleanup, dry, it is 4.4% to calculate polar polypropylene grafting rate.
Claims (7)
1. a kind of preparation method of polar polypropylene, which is characterized in that include the following steps：
A, polypropylene, initiator and grafted monomers are placed in reaction kettle；
B, propylene is passed through into step A, heating is forced into propylene and reaches supercriticality, carries out graft modification reaction, reaction temperature
It is 91-130 DEG C to spend, reaction pressure 4.5-7.0MPa, reaction time 0.1-10h；
C, release cools down after graft reaction, purification, dry, obtained polar polypropylene；
The initiator total amount is the 2-9% of polypropylene quality.
2. the preparation method of polar polypropylene according to claim 1, it is characterised in that the polypropylene is homopolymerization poly- third
Alkene or Propylene polymerization polypropylene.
3. the preparation method of polar polypropylene according to claim 1, it is characterised in that the initiator is selected from by mistake
At least one of group that Benzoyl Oxide, dicumyl peroxide, azodiisobutyronitrile form.
4. the preparation method of polar polypropylene according to claim 2, it is characterised in that the initiator is selected from by mistake
At least one of group that Benzoyl Oxide, dicumyl peroxide, azodiisobutyronitrile form.
5. the preparation method of the polar polypropylene according to any one in Claims 1 to 4, it is characterised in that the grafting
Monomer is selected from by acrylic acid, butyl acrylate, maleic anhydride, butyl methacrylate, methacrylic acid, styrene, methyl
At least one of group that methyl acrylate, ethyl acrylate, three glycerol acrylate of pentaerythrite form.
6. the preparation method of the polar polypropylene according to any one in Claims 1 to 4, it is characterised in that the grafting
Monomer total amount is the 20-30% of polypropylene quality.
7. the preparation method of polar polypropylene according to claim 5, it is characterised in that the grafted monomers total amount is poly-
The 20-30% of propylene quality.
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|---|---|---|---|---|
| CN1486998A (en) * | 2003-07-24 | 2004-04-07 | 华东理工大学 | Supercritical CO2 medium process of preparing unsaturated organic acid grafted polypropylene |
| CN101386668A (en) * | 2008-10-30 | 2009-03-18 | 湘潭大学 | Method for preparing acrylic acid-grafted polypropylene by supercritical carbon dioxide |
| CN102863588A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | Method for modifying polypropylene by supercritical carbon dioxide assisted solid phase grafting |
| CN104151499A (en) * | 2014-07-31 | 2014-11-19 | 华南理工大学 | Preparation method of printable polypropylene material |
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| CN1486998A (en) * | 2003-07-24 | 2004-04-07 | 华东理工大学 | Supercritical CO2 medium process of preparing unsaturated organic acid grafted polypropylene |
| CN101386668A (en) * | 2008-10-30 | 2009-03-18 | 湘潭大学 | Method for preparing acrylic acid-grafted polypropylene by supercritical carbon dioxide |
| CN102863588A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | Method for modifying polypropylene by supercritical carbon dioxide assisted solid phase grafting |
| CN104151499A (en) * | 2014-07-31 | 2014-11-19 | 华南理工大学 | Preparation method of printable polypropylene material |
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