CN106032398A - A preparing method of long-chain branched polypropylene - Google Patents
A preparing method of long-chain branched polypropylene Download PDFInfo
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Abstract
A preparing method of long-chain branched polypropylene is provided. The method includes a) weighing 100 parts by weight of polypropylene, 0.01-0.4 part by weight of an initiator, 0.1-0.3 part by weight of an antioxidant, and 1-10 parts by weight of an acrylate monomer with multiple functional groups, b) adding the initiator, the antioxidant and the acrylate monomer with multiple functional groups into an organic solvent, premixing to obtain a premix solution, and mixing the premix solution with the polypropylene to obtain a mixture, and c) adding the mixture into an extruder, feeding supercritical carbon dioxide from a 1/5-1/3 point of a screw of the extruder, melting, and extruding to obtain the long-chain branched polypropylene. Through feeding the supercritical carbon dioxide into the screw, the actual reaction temperature is greatly reduced, and the branching capability of the acrylate monomer with the multiple functional groups is greatly improved, thus significantly improving the polypropylene melt strength. The invention also provides the long-chain branched polypropylene.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly relate to long-chain branching polypropylene of a kind of high fondant-strength and preparation method thereof.
Background technology
At present, worldwide, the yield of polypropylene (PP) is only second to polyethylene (PE) and polrvinyl chloride (PVC), applies quite varied.Compared with other general-purpose thermoplastic plastic, the feature such as PP has that price is low, density is little, processing nontoxic, easy, resistance to chemical attack and good mechanical performance.But, the molecular structure of PP be linear structure, softening point and fusing point very close to, melt strength is relatively low, thus when causing its thermoforming, products thickness is uneven, high speed extrusion coating time edge curl and contraction and the abscess when extrusion foaming subside, this greatly limits the range of application of PP.In order to improve polypropylene competitiveness in plastic applications, need to improve its melt strength.
High melt strength, propylene (HMSPP) is a kind of Novel polypropylene material that is too low for PP melt strength and that develop.Can by improve polyacrylic relative molecular mass, widen molecular weight distribution and introduce long chain branched obtain HMSPP.The method usually introducing long chain branched is more effective.Have at present and prepare HMSPP by melt grafting.The patent application of such as Publication No. CN1986589A discloses the preparation method of a kind of high bath strength acrylic resin, and it uses the polyacrylic method of acrylic ester compound grafting with melt extrusion to obtain HMSPP.
But, the reaction temperature in this extrusion by melting two to four district is above 200 DEG C, and this easily induces PP strand that β fracture occurs, and causes the degraded of PP resin, thus has influence on the combination property of product.
Summary of the invention
For the problems referred to above, it is an object of the invention to provide less long-chain branching polypropylene and preparation method thereof of degrading in a kind of course of reaction, to solve technical problem in prior art.
The present invention provides the preparation method of a kind of long-chain branching polypropylene, and it comprises the steps:
A weighs polypropylene 100 weight portion, initiator 0.01～0.4 weight portion, and antioxidant 0.1～0.3 weight portion, with multi-functional acrylate monomer 1～10 weight portion；
B by described initiator, antioxidant, add premix in organic solvent with multi-functional acrylate monomer and obtain premixed solution, then premixed solution and polypropylene are mixed to get mixture；
Described mixture is added in an extruder by c, and is passed through the carbon dioxide of above-critical state at the 1/5～1/3 of the screw rod of extruder, melt extrudes and obtains long-chain branching polypropylene.
Organic solvent described in step b is at least one in acetone, ethanol, chloroform, and described organic solvent is 1:50～1:150 with the weight ratio of described initiator.
In step c, the temperature in the first half district of screw rod is 190 DEG C～210 DEG C, and the temperature in the later half district of screw rod is 150 DEG C～190 DEG C.
Described is 1%～5% with polyacrylic percent grafting described in multi-functional acrylate monomer fusion-grafting.
The quality of the carbon dioxide of above-critical state described in step c accounts for the 5%～15% of the gross mass of described mixture, and the injection pressure of the carbon dioxide of described above-critical state is 8MPa～20MPa.
Step c is passed through at the 1/4 of the screw rod of extruder the carbon dioxide of above-critical state.
Described polypropylene be HOPP, COPP or both with arbitrary proportion mixing blend, described polyacrylic melt index is 0.1g/10min～50g/10min.
Described initiator is at least one in dibenzoyl peroxide, cumyl peroxide, peroxy dicarbonate double (4-tert-butyl group caproic acid), cumyl hydroperoxide, di-t-butyl peroxide, peroxy dicarbonate double 2-ethylhexoate, peroxide acetic acid butyl ester.
Described antioxidant is four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester, N, N'-pair-(3-(3, 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, sulfur is for the double [3-(3 of diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester], three [2, 4-di-tert-butyl-phenyl] at least one in phosphite ester, described is trimethylolpropane trimethacrylate with multi-functional acrylate monomer, pentaerythritol triacrylate, 1, 6-hexanediyl ester, 1, at least one in 4-butanediol diacrylate.
The present invention also provides for a kind of long-chain branching polypropylene using above-mentioned preparation method to obtain, and the melt strength of described long-chain branching polypropylene is 19CN～31CN, and melt index is 2.0g/10min～5.5g/10min.
Compared to prior art, this method is by being passed through the carbon dioxide of above-critical state at the 1/5 of described screw rod～1/3, real reaction temperature is made to be greatly reduced, substantially inhibit polyacrylic degraded in course of reaction, substantially increase the grafting ability with multi-functional acrylate monomer, thus significantly improve polyacrylic melt strength.Concrete, in course of reaction, the carbon dioxide of above-critical state increases the free volume of melt polypropylene, effectively reduces the cage effect of reaction member, adds the reaction probabilities of reaction member, thus improves percent grafting；Meanwhile, the carbon dioxide of above-critical state possesses the density of liquid and the diffusion coefficient of gas, can increase, as the carrier of reaction member, the probability reacted to each other；In addition, the CO 2 reduction of the above-critical state viscosity of melt polypropylene, thus reduce reaction temperature, restrained effectively the β fracture in polypropylene molecular chain, thus obtain that percent grafting is high, degradation rate is low, melt index is low and the long-chain branching polypropylene of high fondant-strength.The method technique is simple, energy consumption is low, and gained long-chain branching polypropylene all shows good characteristic at aspects such as color and luster, processing characteristics and mechanical properties.The present invention also provides for the long-chain branching polypropylene prepared by this preparation method a kind of.
Detailed description of the invention
Below in conjunction with embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
The invention provides the preparation method of a kind of long-chain branching polypropylene, it comprises the steps:
A weighs polypropylene 100 weight portion, initiator 0.01～0.4 weight portion, and antioxidant 0.1～0.3 weight portion, with multi-functional acrylate monomer 1～10 weight portion；
B by described initiator, antioxidant, add in organic solvent mixing in advance with multi-functional acrylate monomer and obtain premixed solution, then premixed solution and polypropylene are mixed to get mixture；
Described mixture is added in an extruder by c, and is passed through the carbon dioxide of above-critical state at the 1/5～1/3 of the screw rod of extruder, melt extrudes and obtains long-chain branching polypropylene.
In step a, described polypropylene can be HOPP, COPP or both with arbitrary proportion mixing blend, described polyacrylic melt index is 0.1g/10min～50g/10min.Described initiator is for causing with multi-functional acrylate monomer and polyacrylic graft reaction.Described initiator can be at least one in dibenzoyl peroxide, cumyl peroxide, peroxy dicarbonate double (4-tert-butyl group caproic acid), cumyl hydroperoxide, di-t-butyl peroxide, peroxy dicarbonate double 2-ethylhexoate, peroxide acetic acid butyl ester.Described antioxidant can be four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3; 5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester, N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, sulfur is for the double [3-(3 of diethylene; 5-di-tert-butyl-hydroxy phenyl) propionic ester], at least one in three [2,4-di-tert-butyl-phenyl] phosphite ester.Described with multi-functional acrylate monomer can be trimethylolpropane trimethacrylate, pentaerythritol triacrylate, 1, at least one in 6-hexanediyl ester, BDO diacrylate.
In stepb, by high-speed mixer, premixed solution and polypropylene can be mixed to get mixture.Described organic solvent is at least one in acetone, ethanol, chloroform.Described organic solvent is 1:50～1:150 with the weight ratio of described initiator.
In step c, described mixture can be added in extruder from charging aperture with the speed of 1kg/h～10kg/h.The quality of the carbon dioxide of described above-critical state accounts for the 5%～15% of the gross mass of described mixture.The purity of the carbon dioxide of described above-critical state is 99.9%.The injection pressure of the carbon dioxide of described above-critical state is 8MPa～20MPa.The temperature in the first half district of the screw rod of described extruder is 190 DEG C～210 DEG C, and the temperature in the later half district of screw rod is 150 DEG C～190 DEG C.
Under the effect of initiator, described with multi-functional acrylate monomer and described polypropylene generation melting graft reaction.Owing to being passed through the carbon dioxide of above-critical state at the 1/5 of described screw rod～1/3 so that real reaction temperature is greatly reduced, thus substantially inhibits polyacrylic degraded in course of reaction, and then improves the percent grafting with multi-functional acrylate monomer.Preferably, the carbon dioxide of above-critical state it is passed through at the 1/4 of described screw rod, the most both can guarantee that polyacrylic before being passed through the carbon dioxide of above-critical state fully melting and the preliminary mixing of each component in mixture, also can guarantee that the carbon dioxide of above-critical state has the sufficient time dispersed and is dissolved in mixture after being passed through the carbon dioxide of above-critical state simultaneously, thus can more promote the carrying out of graft reaction compared with fully reducing the reaction temperature in the later half district of screw rod.Described is 1%～5% with polyacrylic percent grafting described in multi-functional acrylate monomer fusion-grafting.
The present invention also provides for the above-mentioned preparation method of a kind of employing and obtains long-chain branching polypropylene.The melt strength of described long-chain branching polypropylene is 19CN～31CN, and melt index is 2.0g/10min～5.5g/10min.
Compared to prior art, this method is by being passed through the carbon dioxide of above-critical state at the 1/5 of described screw rod～1/3, real reaction temperature is greatly reduced, and (temperature in the first half district of screw rod is 190 DEG C～210 DEG C, the temperature in the later half district of screw rod is 150 DEG C～190 DEG C), substantially inhibit polyacrylic degraded in course of reaction, substantially increase the grafting ability with multi-functional acrylate monomer, thus significantly improve polyacrylic melt strength.Concrete, in course of reaction, the carbon dioxide of above-critical state increases the free volume of melt polypropylene, effectively reduces the cage effect of reaction member, adds the reaction probabilities of reaction member, thus improves percent grafting；Meanwhile, the carbon dioxide of above-critical state possesses the density of liquid and the diffusion coefficient of gas, can increase, as the carrier of reaction member, the probability reacted to each other；In addition, the CO 2 reduction of the above-critical state viscosity of melt polypropylene, thus reduce reaction temperature, restrained effectively the β fracture in polypropylene molecular chain, thus obtain that percent grafting is high, degradation rate is low, melt index is low and the long-chain branching polypropylene of high fondant-strength.The method technique is simple, energy consumption is low, and gained long-chain branching polypropylene all shows good characteristic at aspects such as color and luster, processing characteristics and mechanical properties.
Below in conjunction with specific embodiment, the preparation method of the long-chain branching polypropylene of the present invention is illustrated:
Embodiment 1:
Weigh 0.05 part of dibenzoyl peroxide, 0.1 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and 4 part 1,6-hexanediyl ester；
By dibenzoyl peroxide, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, 1,6-hexanediyl ester adds premixing in 5mL acetone and obtains premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, acetone is 1:80 with the weight ratio of initiator dibenzoyl peroxide；
Add mixture in extruder；Wherein, screw speed is set to 30r/min, and the first half district temperature of screw rod is set to 190 DEG C, and the later half district temperature of screw rod is set to 160 DEG C；Injecting the carbon dioxide of 5 weight portion above-critical states at the 1/4 of screw rod, injection pressure is set to 10MPa, and extruding pelletization obtains long-chain branching polypropylene.
Embodiment 2:
Weigh 0.05 part of cumyl peroxide, 0.1 part of sulfur for diethylene double [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] and 6 parts of trimethylolpropane trimethacrylates；
By cumyl peroxide, sulfur for the double [3-(3 of diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester] and trimethylolpropane trimethacrylate add premixing in 3mL ethanol and obtain premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, ethanol is 1:50 with the weight ratio of initiator cumyl peroxide；
Add mixture in extruder；Wherein, screw speed is set to 70r/min, and the first half district temperature of screw rod is set to 200 DEG C, and the later half district temperature of screw rod is set to 160 DEG C；Injecting the carbon dioxide of 10 weight portion above-critical states at the 1/3 of screw rod, injection pressure is set to 12MPa, and extruding pelletization obtains long-chain branching polypropylene.
Embodiment 3:
Weigh 0.2 part of di-t-butyl peroxide, 0.3 part of N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and 10 parts of BDO diacrylates；
By di-t-butyl peroxide, N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and 1; 4-butanediol diacrylate adds premixing in 25mL acetone and obtains premixed solution; afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer; mixing 10min with the speed of 300r/min and obtain mixture, wherein, acetone is 1:100 with the weight ratio of initiator di-t-butyl peroxide；
Add mixture in extruder；Wherein, screw speed is set to 60r/min, and the first half district temperature of screw rod is set to 210 DEG C, and the later half district temperature of screw rod is set to 170 DEG C；Injecting the carbon dioxide of 12 weight portion above-critical states at the 1/5 of screw rod, injection pressure is set to 14MPa, and extruding pelletization obtains long-chain branching polypropylene.
Embodiment 4:
Weigh 0.08 part of di-t-butyl peroxide, 0.3 part of N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and 10 parts of BDO diacrylates；
By di-t-butyl peroxide, N; N'-pair-(3-(3; 5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and 1; 4-butanediol diacrylate adds premixing in 8mL chloroform and obtains premixed solution; afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer; mixing 10min with the speed of 300r/min and obtain mixture, wherein, chloroform is 1:150 with the weight ratio of initiator di-t-butyl peroxide；
Add mixture in extruder；Wherein, screw speed is set to 90r/min, and the first half district temperature of screw rod is set to 200 DEG C, and the later half district temperature of screw rod is set to 150 DEG C；Injecting the carbon dioxide of 10 weight portion above-critical states at the 1/4 of screw rod, injection pressure is set to 10MPa, and extruding pelletization obtains long-chain branching polypropylene.
Embodiment 5:
Weigh 0.1 part of peroxide acetic acid butyl ester, 0.5 part of β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester and 8 parts of pentaerythritol triacrylates；
By peroxide acetic acid butyl ester, part β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid octadecanol ester and pentaerythritol triacrylate add premixing in 8mL ethanol and obtain premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, ethanol is 1:60 with the weight ratio of initiator peroxide acetic acid butyl ester；
Add mixture in extruder；Wherein, screw speed is set to 70r/min, and the first half district temperature of screw rod is set to 210 DEG C, and the later half district temperature of screw rod is set to 160 DEG C；Injecting the carbon dioxide of 8 weight portion above-critical states at the 1/5 of screw rod, injection pressure is set to 12MPa, and extruding pelletization obtains long-chain branching polypropylene.
Embodiment 6:
Weigh 0.1 part of peroxy dicarbonate double (4-tert-butyl group caproic acid), 0.3 part of three [2,4-di-tert-butyl-phenyl] phosphite ester and 10 part of penta tetrol triacrylate；
By double for peroxy dicarbonate (4-tert-butyl group caproic acid), three [2,4-di-tert-butyl-phenyl] phosphite ester and penta tetrol triacrylate add premixing in 8mL chloroform and obtain premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, chloroform is 1:120 with the weight ratio of initiator peroxy dicarbonate double (4-tert-butyl group caproic acid)；
Add mixture in extruder；Wherein, screw speed is set to 100r/min, and the first half district temperature of screw rod is set to 190 DEG C, and the later half district temperature of screw rod is set to 150 DEG C；Injecting the carbon dioxide of 15 weight portion above-critical states at the 1/3 of screw rod, injection pressure is set to 18MPa, and extruding pelletization obtains long-chain branching polypropylene.
Embodiment 7:
Weigh 0.05 part of cumyl hydroperoxide, 0.1 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and 8 parts of trimethylolpropane trimethacrylates；
By cumyl hydroperoxide, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and trimethylolpropane trimethacrylate add premixing in 4mL acetone and obtain premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, acetone is 1:70 with the weight ratio of initiator cumyl hydroperoxide；
Add mixture in extruder；Wherein, screw speed is set to 80r/min, and the first half district temperature of screw rod is set to 200 DEG C, and the later half district temperature of screw rod is set to 170 DEG C；Injecting the carbon dioxide of 7 weight portion above-critical states at the 1/4 of screw rod, injection pressure is set to 12MPa, and extruding pelletization obtains long-chain branching polypropylene.
Embodiment 8:
Weigh the double 2-ethylhexoate of 0.15 part of peroxy dicarbonate, 0.2 part of sulfur for diethylene double [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] and 4 part 1,6-hexanediyl ester；
By double for peroxy dicarbonate 2-ethylhexoates, sulfur for the double [3-(3 of diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester] and 1,6-hexanediyl ester adds premixing in 19mL ethanol and obtains premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, the weight ratio of ethanol 2-ethylhexoate double with initiator peroxy dicarbonate is 1:100；
Add mixture in extruder；Wherein, screw speed is set to 90r/min, and the first half district temperature of screw rod is set to 200 DEG C, and the later half district temperature of screw rod is set to 150 DEG C；Injecting the carbon dioxide of 12 weight portion above-critical states at the 1/4 of screw rod, injection pressure is set to 16MPa, and extruding pelletization obtains long-chain branching polypropylene.
Comparative example 1:
Weigh 0.05 part of dibenzoyl peroxide, 0.1 part of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and 10 parts of BDO diacrylates；
By dibenzoyl peroxide, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester and 1,4-butanediol diacrylate adds premixing in 5mL acetone and obtains premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, acetone is 1:80 with the weight ratio of initiator dibenzoyl peroxide；
Add mixture in extruder；Wherein, screw speed is set to 50r/min, and screw rod first half district temperature is set to 210 DEG C, and screw rod later half district temperature is set to 190 DEG C；It is not injected into the carbon dioxide of above-critical state, extruding pelletization.
Comparative example 2:
Weigh 0.1 part of cumyl peroxide, 0.2 part of sulfur for diethylene double [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester and 6 parts of trimethylolpropane trimethacrylates；
By cumyl peroxide, sulfur for the double [3-(3 of diethylene, 5-di-tert-butyl-hydroxy phenyl) propionic ester and trimethylolpropane trimethacrylate add premixing in 8mL ethanol and obtain premixed solution, afterwards 100 parts of polypropylene and premixed solution are put into high-speed mixer, mix 10min with the speed of 300r/min and obtain mixture, wherein, ethanol is 1:60 with the weight ratio of initiator cumyl peroxide；
Add mixture in extruder；Wherein, screw speed is set to 40r/min, and screw rod first half district temperature is set to 190 DEG C, and screw rod later half district temperature is set to 190 DEG C；It is not injected into the carbon dioxide of above-critical state, extruding pelletization.
Product obtained by embodiment 1 to 8, comparative example 1 and 2 is carried out mechanical property, melt index and melt strength test, the results are shown in Table 1.Wherein, tensile property test: use Instron5567 universal testing machine；Impact strength is tested: use XJ-50Z combination type shock machine；Melt index is tested: using RL-11B Melt Flow Rate Measurer, the condition of test is temperature 230 DEG C, load 2.16kg；Melt strength is tested: use ATS Faar melt strength tester.
Table 1
From table 1, relative to comparative example 1 and 2, mechanical property and the melt strength of the long-chain branching polypropylene that embodiment 1 to 8 obtains all improve, and melt index reduces.This illustrates that the long-chain branching polypropylene that this preparation method obtains has excellent processing characteristics and mechanical property, beneficially commercial application.
The above is the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for long-chain branching polypropylene, it comprises the steps:
A weighs polypropylene 100 weight portion, initiator 0.01～0.4 weight portion, antioxidant 0.1～0.3 weight
Part, with multi-functional acrylate monomer 1～10 weight portion；
B is by described initiator, antioxidant, add in organic solvent pre-with multi-functional acrylate monomer
Mixing obtains premixed solution, then premixed solution and polypropylene are mixed to get mixture；
Described mixture is added in an extruder by c, and is passed through super facing at the 1/5～1/3 of the screw rod of extruder
The carbon dioxide of boundary's state, melt extrudes and obtains long-chain branching polypropylene.
2. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that step
Described in rapid b, organic solvent is at least one in acetone, ethanol, chloroform, and described organic solvent is with described
The weight ratio of initiator is 1:50～1:150.
3. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that step
In rapid c, the temperature in the first half district of screw rod is 190 DEG C～210 DEG C, the temperature in the later half district of screw rod be 150 DEG C～
190℃。
4. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that institute
Stating with polyacrylic percent grafting described in multi-functional acrylate monomer fusion-grafting is 1%～5%.
5. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that step
Described in rapid c, the quality of the carbon dioxide of above-critical state accounts for the 5%～15% of the gross mass of described mixture, institute
The injection pressure of the carbon dioxide stating above-critical state is 8MPa～20MPa.
6. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that step
Rapid c is passed through at the 1/4 of the screw rod of extruder the carbon dioxide of above-critical state.
7. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that institute
State the blend that polypropylene is HOPP, COPP or both mix with arbitrary proportion, described poly-
The melt index of propylene is 0.1g/10min～50g/10min.
8. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that described
Initiator be dibenzoyl peroxide, cumyl peroxide, peroxy dicarbonate double (4-tert-butyl group caproic acid),
Cumyl hydroperoxide, di-t-butyl peroxide, peroxy dicarbonate double 2-ethylhexoate, peroxidating second
At least one in tert-butyl acrylate.
9. the preparation method of a long-chain branching polypropylene as claimed in claim 1, it is characterised in that described
Antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3,5-bis-uncles
Butyl-4-hydroxy phenyl) propanoic acid octadecanol ester, N, N'-be double-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl
Base) hexamethylene diamine, sulfur for diethylene double [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], three [2,4-bis-
Tert-butyl-phenyl] at least one in phosphite ester, described is three with multi-functional acrylate monomer
Hydroxymethyl-propane triacrylate, pentaerythritol triacrylate, 1,6-hexanediyl ester, Isosorbide-5-Nitrae-
At least one in butanediol diacrylate.
10. use the long-chain branching polypropylene obtained such as claim 1 to 9 any one preparation method,
It is characterized in that, the melt strength of described long-chain branching polypropylene is 19CN～31CN, and melt index is
2.0g/10min～5.5g/10min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106750989A (en) * | 2016-11-22 | 2017-05-31 | 广东联塑科技实业有限公司 | A kind of low temperature resistant high rigidity PPR pipe and preparation method thereof |
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| 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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