Summary of the invention
In the existing high density polyethylene communication cable insulating material production technology, the homogeneity and the over-all properties of blend level high-density polyethylene communication cable insulating material are relatively poor; The molecular weight distribution of the communication cable insulating material of bigger device production is unimodal distribution, and its processing fluidity is not good enough, uses to be subjected to certain restriction on high speed insulating core production line.The present invention relates to the manufacturing process of exploitation high density polyethylene communication cable insulating material on the bigger device that adopts Mitsui Chemicals high density polyethylene(HDPE) technology, can produce polymerization-grade double-peak high-density polytene communication cable insulating material, have good homogeneous and over-all properties and processing fluidity simultaneously.
As everyone knows, Mitsui Chemicals high density polyethylene(HDPE) technology adopts low pressure slurry method technology, can produce HDPE and MDPE.Ethene, hydrogen, comonomer, thinner and super high activity catalyst enter reactor, polymerization reaction take place under slurry condition, the polymer property automatic control system can be controlled quality product effectively, can produce the product of narrow or wide molecular weight distribution, and density is 930~970kg/m
3, melting index 0.01~50g/10min.
Mitsui Chemicals high density polyethylene(HDPE) technology, be with high-purity ethylene (99.9%, volume fraction) is main raw material, propylene or butene-1 are comonomer, hexane is a solvent, uses effective catalyst Ziegler-Natta catalyst (titanous chloride and aluminum alkyls), under the condition of 78~86 ℃ of service temperatures, pressure 0.20~0.80MPa, carry out two still low-pressure polymerizations, general about 2 hours of the reaction times.The polyethylene slurry of polymerization output is through separating drying, granulation and being packaged to be the polyethylene finished product.In order to obtain communication cable insulating material, in dried polyethylene powders, add communication cable insulating material special assistant prescription usually and carry out granulation.The hydrogen amount that adjusting adds, the molecular weight of control product is regulated the comonomer propylene or the butene-1 amount that add, controls the density of product, thereby obtains the product of the various different trades mark.The operating method that adopts on its device can be carried out the conversion of two still serial or parallel connection polymerization flow processs, produces the product of the different trades mark.
The manufacture method of double-peak high-density polytene communication cable insulating material involved in the present invention on existing Mitsui Chemicals high density polyethylene(HDPE) process unit, adopts two slurry polymerization still cascade reaction flow processs.The present invention transforms existing procedure design, and promptly catalyzer only adds in first reactor, and only adds ethene, hydrogen in first reactor, does not add the comonomer butene-1, and the polymkeric substance of production is the low molecular weight polyethylene homopolymer; In second reactor, do not add catalyzer, add ethene, hydrogen and comonomer butene-1 and carry out polyreaction, the comonomer butene-1 is aggregated in the product on the High molecular weight polyethylene molecular chain.Change the add-on of hydrogen, the molecular weight distribution of regulating polymkeric substance in two stills, the polymericular weight of controlling first reactor is lower, and the polymericular weight of second reactor is higher, thereby obtains the polyethylene product that molecular weight is bimodal distribution.
Technical scheme of the present invention is as follows:
A kind of manufacture method of double-peak high-density polytene communication cable insulating material, on Mitsui Chemicals high density polyethylene(HDPE) process unit, use efficient Ziegler-Natta catalyst, under 78~86 ℃ of service temperatures, pressure 0.20~0.80MPa condition, adopt two slurry polymerization still series connection polyreaction flow processs, it is characterized in that: do not add the comonomer butene-1 in first reactor, by polymerization single polymerization monomer ethene and hydrogen under catalyst action, carry out first section polyreaction, obtain the low molecular weight polyethylene homopolymer; Do not add catalyzer in second reactor, add ethene, hydrogen and comonomer butene-1 and carry out second section polyreaction, the comonomer butene-1 is aggregated on the High molecular weight polyethylene molecular chain of generation; The add-on of control hydrogen makes hydrogen/ethylene ratio (volume ratio, H
2/ C "
2, vol%) in first reactor 〉=1.0, in second reactor≤0.6.
The present invention adopts two still serial operation flow processs of Mitsui Chemicals high density polyethylene(HDPE) technology, can realize the production of bimodal polyethylene resins, and resulting product had both kept the intensity of HDPE, had improved the processing characteristics of product again.When producing double-peak high-density polytene, polyreaction still adopts the high reactivity Ziegler-Natta catalyst, with the hexane is dispersion medium (solvent), under the essentially identical situation of other operational conditions, change first still, the hydrogen add-on of second still, reach and regulate first still, the purpose of the molecular weight of the second still polymkeric substance, make the molecular weight of the polymkeric substance that first still and second still produced present different distributions, the first still polymkeric substance is the low molecular weight polyethylene homopolymer, polymerization has the High molecular weight polyethylene of butene-1 on second still generation molecular chain, through two still series connection polyethylene that polyreaction produced, its molecular weight is typical bimodal distribution state; The comonomer butene-1 adopts first still not add and the mode that only adds at second still, control the density of the polymkeric substance of two stills reaction generation, making the first still polymkeric substance is the lower molecular weight high density polyethylene(HDPE), the second still polymkeric substance be high molecular than new LDPE (film grade), the density of product is controlled in the specific scope.When the product granulation, add communication cable insulating material special assistant prescription, make needed double-peak high-density polytene communication cable insulating material.
Improved typical process flow is:
In first reactor, add catalyzer, and only add ethene, hydrogen do not add the comonomer butene-1, carries out homopolymerization, obtains lower molecular weight high density polyethylene(HDPE) homopolymer; In second reactor, do not add catalyzer, and add ethene, hydrogen and comonomer butene-1, the comonomer butene-1 is aggregated in the product on the High molecular weight polyethylene molecular chain, obtain high molecular than ldpe copolymer, as shown in Figure 1.
Concrete technological operation of the present invention is:
According to the present invention, on Mitsui Chemicals high density polyethylene(HDPE) process unit, add ethene, hydrogen, catalyzer and solvent hexane at first reactor, 83 ± 3 ℃ of still temperature, still is pressed under the 0.55-0.65Mpa and is carried out homopolymerization, and the ethene flow is 1.5-10.0t/h, hydrogen/ethylene ratio (H
2/ C "
2, vol%) be 1.0-5.5, react and enter the first slurries still after 2--4 hour.The resulting low molecular weight polyethylene homopolymer of first reactor enters second reactor from the first slurries still, and second reactor adds ethene, butene-1 and hydrogen, does not add catalyzer and carries out copolyreaction; 80 ± 2 ℃ of still temperature, still is pressed 0.2-0.4Mpa, and the ethene flow is 1.0-8.0t/h, hydrogen/ethylene ratio (H
2/ C "
2, vol%) being 0.01-0.60, the butene-1 flow is 30-200kg/h, reacts 2--4 hour.After two still polyreactions are finished, according to existing identical step and the method for technology, material enters the second slurries still, enter flash tank then, flash distillation enters centrifugal drier after finishing, add communication cable insulating material special assistant prescription at last and carry out extruding pelletization, make the double-peak high-density polytene communication cable insulating material.
Control the hydrogen add-on of first reactor and second reactor, promptly regulate the hydrogen/ethylene ratio of first reactor and second reactor, be may command first reactor and the resulting polymericular weight of second reactor, produce the bimodal polyethylene product of different molecular weight and distribution thereof.Hydrogen/ethylene ratio is big, and polymericular weight is then low, otherwise hydrogen/ethylene ratio is little, and polymericular weight is then high.Generally, the present invention is with hydrogen/ethylene ratio (H of first reactor
2/ C "
2, vol%) being controlled in the scope of high value 1.0-5.5, the molecular weight of polyethylene that first reactor is obtained is lower; Hydrogen/ethylene ratio (H of second reactor
2/ C "
2, vol%) being controlled in the scope of smaller value 0.01-0.60, the poly molecular weight that second reactor is obtained is higher, and this control can make the molecular weight distribution of the finished product high and low two peak values occur.Be different from the molecular weight and the distribution thereof of the existing trade mark product that adopts Mitsui Chemicals high density polyethylene(HDPE) explained hereafter according to the resulting product of the present invention, but presenting typical bimodal distribution state, low-molecular weight polymer wherein can be product good processing flowability is provided.For obtaining polymerization-grade double-peak high-density polytene communication cable insulating material, and have good homogeneous and over-all properties and processing fluidity, hydrogen/ethylene ratio (H of first reactor and second reactor
2/ C "
2, preferable range vol%) is respectively 2.5-3.5 and 0.16-0.35.
According to the present invention program, the add-on of butene-1 can be regulated the density of product in second reactor, thereby produces the bimodal polyethylene product of different environmental stress cracking resistances.Add the comonomer butene-1 in second reactor, the density that can regulate the high density polyethylene(HDPE) product is controlled in the specified range that is fit to needs the density of product.Butene-1 is aggregated on the second reactor High molecular weight polyethylene molecular chain simultaneously, and the environmental stress cracking resistance of product is significantly improved.Increase the add-on of butene-1, the butene-1 side chain that is aggregated on the sub polyethylene subchain increases, and twine mutually between polymer molecule to strengthen, so the environmental stress cracking resistance of polymkeric substance is improved.For making polymerization-grade double-peak high-density polytene communication cable insulating material, the present invention is on the device of 1.0-8.0t/h at the second reactor ethene flow, and the butene-1 flow of adding is 30-200kg/h, and its preferable range is 94-120kg/h.
The resulting high density polyethylene(HDPE) product according to the present invention, its molecular weight is bimodal distribution, the homogeneity and the over-all properties of product increase significantly, processing fluidity has obtained tangible improvement, and every index reaches the YD/T760-95 of the Post and Telegraph Department " city communication cable polyolefin insulation material " standard fully.
Blend level high-density polyethylene communication cable insulating material and polymerization-grade double-peak high-density polytene product according to the present invention are carried out the performance comparison test, and concrete data see Table 1.
Table 1 polymerization-grade double-peak high-density polytene communication cable insulating material with
The performance comparison of blend level high-density polyethylene communication cable insulating material
Can find out that from table 1 homogeneity and the over-all properties of blend level high-density polyethylene communication cable insulating material are relatively poor, the homogeneity and the over-all properties of product of the present invention are significantly increased.
The processing characteristics of the unimodal high density polyethylene communication cable insulating material of polymerization-grade and processing characteristics according to double-peak high-density polytene product of the present invention are compared, and comparing result is seen Fig. 2.
As can be seen from Figure 2, the processing characteristics of the unimodal high density polyethylene communication cable insulating material of polymerization-grade is not good enough, and the processing fluidity of product of the present invention is improved.
The performance of product of the present invention is tested, and concrete data see Table 2.
The salient features measured value of table 2 polymerization-grade double-peak high-density polytene communication cable insulating material
Can find out from table 1,2, the mechanical property of polymerization-grade double-peak high-density polytene communication cable insulating material, environmental stress cracking resistance is greatly improved, and every indexs such as other electrical properties reach the YD/T760-95 of the Post and Telegraph Department " city communication cable polyolefin insulation material " standard fully.
Embodiment
Embodiment one
Manufacture method according to double-peak high-density polytene communication cable insulating material involved in the present invention, on Mitsui technology high density polyethylene device, under Ziegler-Natta catalyst (titanous chloride and aluminum alkyls) effect, two slurry polymerization stills are together in series carry out polyreaction.Add catalyzer in first reactor, and only add ethene hydrogen and do not add the comonomer butene-1, reacted 2 hours, the polymkeric substance of generation is the low molecular weight polyethylene homopolymer; Do not add catalyzer in second reactor, and add ethene, hydrogen and comonomer butene-1, the comonomer butene-1 is aggregated in the product on the High molecular weight polyethylene molecular chain, reacted 2 hours, the polymkeric substance of generation is the High molecular weight polyethylene multipolymer.The concrete controlling of production process parameter of two reactors sees Table 3.
The processing parameter of table 3 embodiment one
The high density polyethylene(HDPE) of producing under above-mentioned controlling of production process parameter adds communication cable insulating material special assistant prescription extruding pelletization after separating drying, can make the double-peak high-density polytene communication cable insulating material.(the experiment lot number: 060528BC) measured value of performance sees Table 4 to specific product.
Table 4 double-peak high-density polytene communication cable insulating material performance measured value
Project |
Testing standard |
Unit |
Standard-required |
Measured value |
Melt flow rate (MFR) (2.16Kg) |
GB/T 3682 |
g/10min |
≤1.0 |
0.70 |
Density |
GB/T 1033 |
g/cm
3 |
0.941~0.959 |
0.956 |
Tensile strength |
GB/T 1040 |
MPa |
≥19 |
28.7 |
Elongation at break |
GB/T 1040 |
% |
≥400 |
1144 |
Resisting environmental stress and cracking (48h)-failure number |
GB/T 1842 |
Individual |
≤2/10 |
0/10 |
Oxidation induction period (200 ℃, the Cu cup) |
GB/T 2951.37 |
min |
≥30 |
>46 |
Specific inductivity (1MHz) |
GB/T 1409 |
|
≤2.40 |
2.26 |
The double-peak high-density polytene communication cable insulating material of being produced is carried out the test of molecular weight and distribution curve thereof, the results are shown in Figure 3 and table 5.
The number-average molecular weight Mn of double-peak high-density polytene communication cable insulating material, weight-average molecular weight Mw, Z-average molecular weight Mz, (Z+1)-average molecular weight Mz+1 see Table 5 respectively among Fig. 3.
Table 5
Sample |
Mn (Daltons) |
Mw (Daltons) |
Mz (Daltons) |
Mz+i (Daltons) |
Polydispersity |
060528BC |
7237 |
122607 |
657311 |
1139213 |
16.940858 |
As can be seen from Figure 3, the molecular weight of double-peak high-density polytene communication cable insulating material and distribution curve thereof obviously have two peak values, illustrate that its molecular weight and distribution thereof are bimodal distribution.On the other hand, numerical value from table 5 as can be known, its heterogeneity index Polydispersity value is 16.94, its molecular weight distribution broad is described, number-average molecular weight Mn has only 7237, illustrate that product has a considerable amount of low-molecular weight polymer compositions, weight-average molecular weight Mw reaches 122607, illustrates that product has a considerable amount of high-molecular weight polymer compositions.The heterogeneity index of general polymerization thing is between 1.5~3.0.
Embodiment two
According to the present invention, change the hydrogen add-on of first reactor and second reactor, promptly change the hydrogen/ethylene ratio of first reactor and second reactor, promptly the polymericular weight of may command first reactor and second reactor is produced the bimodal polyethylene product of different molecular weight and distribution thereof.Change the butylene add-on of second reactor, promptly change the co-monomer content of second reactor, can produce the double-peak high-density polytene product of different environmental stress cracking resistances.
Among the embodiment two, by changing the process control parameter among the embodiment one, the flow of hydrogen/ethylene ratio and butene-1 particularly, can obtain the double-peak high-density polytene product of different molecular weight and distribution thereof and different environmental stress cracking resistances, add the granulation of communication cable insulating material special assistant prescription then, can produce the double-peak high-density polytene communication cable insulating material of different performance.The concrete controlling of production process parameter of present embodiment sees Table 6.
The processing parameter of table 6 embodiment two
The resulting double-peak high-density polytene communication cable insulating material of present embodiment is compared with embodiment one, because at hydrogen/ethylene ratio (H
2/ C "
2Vol%) in the control, present embodiment in first reactor (2.50-3.00) is lower than embodiment one (3.00-3.50), and present embodiment (0.26-0.35) is higher than embodiment one (0.16-0.25) in second reactor, so the molecular weight and the narrow distribution thereof of present embodiment products obtained therefrom, and embodiment one products obtained therefrom broad.On the other hand, because present embodiment butene-1 inlet amount (105-120kg/h) is greater than the inlet amount (94-110kg/h) of embodiment one, therefore the co-monomer content of present embodiment products obtained therefrom is than embodiment one height, shows on the performance to be that the environmental stress cracking resistance of product is good than embodiment one.
As seen, the present invention is on using, and the adjusting of processing parameter can change the performance of product; Otherwise, can come the adjusting process parameter according to the needs of product performance.