CN115895115A - High-crystallinity hydrophilic syndiotactic polypropylene composite material and preparation method thereof - Google Patents
High-crystallinity hydrophilic syndiotactic polypropylene composite material and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 71
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 67
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 58
- 230000008025 crystallization Effects 0.000 claims abstract description 58
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 38
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 25
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 25
- 239000002667 nucleating agent Substances 0.000 claims abstract description 21
- 238000005469 granulation Methods 0.000 claims abstract description 16
- 230000003179 granulation Effects 0.000 claims abstract description 16
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 14
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 abstract description 21
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 21
- 230000001737 promoting effect Effects 0.000 abstract description 8
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 238000012661 block copolymerization Methods 0.000 abstract description 3
- 229920000573 polyethylene Polymers 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Abstract
The invention discloses a high-crystallinity hydrophilic syndiotactic polypropylene composite material and a preparation method thereof; the composite material comprises the following components in parts by weight: 80.0 to 91.1 portions of syndiotactic polypropylene; 0 to 10 portions of polyethylene; 2-10 parts of ethylene-vinyl alcohol copolymer; 0 to 8 portions of homo-polypropylene; 0 to 0.2 percent of nucleating agent; 0.1 to 0.3 percent of antioxidant; 0.1 to 0.3 percent of auxiliary antioxidant. The components are mixed and extruded by a double-screw extruder for granulation to obtain the syndiotactic polypropylene composite material. EVOH has stronger crystallization performance because of containing ethylene chain segments of block copolymerization, and can induce ordered folding of sPP molecular chains, thereby promoting the improvement of sPP crystallization performance. Moreover, EVOH contains a certain proportion of polar groups, so that the composite material can be endowed with better hydrophilic performance. By compounding the EVOH with the effective crystallization promoting components of sPP such as iPP, HDPE and the like, the characteristics of each component are comprehensively utilized, and the crystallization performance of the sPP is expected to be optimized and greatly promoted. The invention not only expands the selection range of the sPP crystallization performance promoter, but also can extend the application field of the sPP.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a high-crystallinity hydrophilic syndiotactic polypropylene composite material and a preparation method thereof.
Background
Syndiotactic polypropylene (sPP) was first isolated from isotactic polypropylene (iPP) and later Evan et al polymerized under the action of a syndiotactic selective metallocene catalyst to obtain sPP of high purity. Compared with iPP, sPP has higher transparency, stronger toughness and elasticity, lower density and rigidity, and certain radiation resistance. However, because methyl groups on two sides of the sPP molecular chain are alternately distributed and the molecular weight distribution is narrow, the movement of the sPP molecular chain has the characteristics of the sPP molecular chain, so that the melting point and the crystallization temperature of the sPP are lower, and the crystallization speed is slow. The lower crystallization temperature of sPP affects the use performance and is difficult to process by conventional equipment. One of the cores for improving the processability and the use properties of sPP is to improve its crystallization properties.
At present, no nucleating agent with obvious effect on promoting sPP crystallization nucleation is found, and in order to improve crystallization performance, a common modification means is to blend polyolefin with higher crystallization temperature to improve the crystallization degree and crystallization temperature of sPP. In the alternative of semi-crystalline polyolefins, iPP and random copolymer polypropylene (rPP) increase the crystallization temperature of sPP with a degree of syndiotacticity of 80 to 90mol% from about 70 ℃ to about 85 ℃ and High Density Polyethylene (HDPE) increases the crystallization temperature of sPP to above 90 ℃ (see patent 202111249433.7 for details). However, few polyolefins have been found to be selectable for improving the crystallinity of sPP and it has been difficult to meet the actual production requirements for sPP articles.
Ethylene-propylene alcohol copolymer (EVOH) is an alcoholysis product of saponification or partial saponification of ethylene-vinyl acetate copolymer (EVA), and is the first industrial production in 1972, and is a good barrier material. The molecular chain of the polymer has both nonpolar ethylene segments and polar group hydroxyl groups, so that EVOH is often blended with other polyolefins to improve the hygroscopicity and the toughness. However, by examining the structure and the crystallization performance of the EVOH, the EVOH has strong crystallization performance due to the fact that the EVOH contains a block copolymerized ethylene segment, and the EVOH is expected to induce ordered folding of sPP molecular chains and further promote improvement of sPP crystallization performance. Moreover, EVOH contains a certain proportion of polar groups, so that the composite material can be endowed with better hydrophilic performance. Therefore, the EVOH is adopted as the crystallization property improving component of the sPP, so that the selection range of the sPP crystallization property promoter is expanded, and the application field of the sPP can be expanded.
More importantly, by compounding the EVOH with the effective crystallization promoting components of sPP such as iPP, HDPE and the like, the characteristics of the components are comprehensively utilized, and the crystallization performance of the sPP is expected to be optimized and greatly promoted.
Disclosure of Invention
The present invention is directed to overcome the above-mentioned disadvantages and drawbacks of the prior art and to provide a hydrophilic syndiotactic polypropylene composite having high crystallinity and a method for preparing the same. The composite material prepared by the preparation process disclosed by the invention has higher crystallinity and crystallization temperature, can solve the problem of difficult processing of syndiotactic polypropylene due to low crystallinity and crystallization temperature, and expands the application of the syndiotactic polypropylene in related fields.
The principle of the invention is as follows:
researches show that the molecular chain of sPP is more difficult to orderly fold in the crystallization process, the nucleation point of the minimum zone formed by only depending on inorganic nucleating agent or small-molecule organic nucleating agent can not continue the crystallization growth under the condition of higher than the blank sPP crystallization temperature, and the crystallization growth can be continued only by virtue of the continuous growth of polyolefin crystal which has better compatibility with the nucleation point and the crystallization temperature of which is higher than about 10-50 ℃ of sPP. The crystallization temperature and melting point of EVOH, HDPE, iPP are higher, the crystallization rate is faster, crystals are formed before sPP is crystallized in the cooling crystallization process, a heterogeneous nucleation point is provided for sPP, and the crystallization starting temperature of sPP is increased. In the actual processing, the crystallization degree and crystallization temperature of the sPP are improved by the cooperation of the nucleating agent. And the EVOH molecular chain contains polar groups which have certain hydrophilic property and can endow the syndiotactic polypropylene composite material with certain hydrophilic property
The invention is realized by the following technical scheme:
the melt flow rate of the syndiotactic polypropylene is 1-20 g/10min (230 ℃,2.16 kg), and the degree of syndiotacticity is more than 80%. Preferably syndiotactic polypropylene having a syndiotacticity of 90% or more and a melt flow rate of 3 to 10g/10 min.
The polyethylene may be High Density Polyethylene (HDPE) or Linear Low Density Polyethylene (LLDPE), preferably high density polyethylene with better crystallization properties. The melt flow rate of the high density polyethylene is 0.1 to 10g/10min (190 ℃,2.16 kg). High density polyethylene having a melt flow rate of about 0.3 to 2g/10min is preferred.
The ethylene content of the ethylene-vinyl alcohol copolymer is less than or equal to 50 percent, and the melt flow rate is 3-15 g/10min (210 ℃,2.16 kg). Preferably an ethylene-propylene alcohol copolymer having an ethylene content of not more than 30% and a melt flow rate of 3 to 15g/10 min.
The melt flow rate of the homopolymerized polypropylene is 20-100 g/10min (230 ℃,2.16 kg), and the isotacticity is more than 95%. Preferably homo-polypropylene with isotacticity of over 97% and melt flow rate of 20-30 g/10min.
The nucleating agent is phosphate polypropylene nucleating agent.
The antioxidant is 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), and the auxiliary antioxidant is 168 (tri [2, 4-di-tert-butylphenyl ] phosphite).
A preparation method of a hydrophilic syndiotactic polypropylene composite material with high crystallization temperature comprises the following steps:
(1) Mixing: sequentially adding syndiotactic polypropylene, high-density polyethylene, ethylene-vinyl alcohol copolymer, homo-polypropylene, nucleating agent, antioxidant and the like into a high-speed mixer for premixing, wherein the mixing temperature is 20-30 ℃, the rotating speed is 200-500 r/min, and the mixing time is 3-5 minutes to obtain a premix of the syndiotactic polypropylene compound;
(2) And (3) double-screw extrusion granulation: and (3) extruding and granulating the premix obtained in the step (1) by using a parallel co-rotating twin-screw extruder with the length-diameter ratio of 40 and the screw diameter of 35mm to obtain the syndiotactic polypropylene compound.
The specific process conditions of the twin-screw extrusion granulation are as follows:
the rotating speed of the feeder is set to be 10-50 revolutions per minute, and the rotating speed of the screw is set to be 100-300 revolutions per minute; the temperature of each section of the extruder is 170-220 ℃, and the syndiotactic polypropylene compound is obtained.
Compared with the prior art, the invention has the following advantages and effects:
(1) EVOH has stronger crystallization performance because of containing ethylene chain segments of block copolymerization, and can induce ordered folding of sPP molecular chains, thereby promoting the improvement of sPP crystallization performance.
(2) EVOH contains a certain proportion of polar groups, and can endow the composite material with better hydrophilic performance. Therefore, the EVOH is adopted as the crystallization property improving component of the sPP, so that the selection range of the sPP crystallization property promoter is expanded, and the application field of the sPP can be expanded.
(3) More importantly, by compounding the EVOH with the effective crystallization promoting components of sPP such as iPP, HDPE and the like, the characteristics of the components are comprehensively utilized, and the crystallization performance of the sPP is expected to be optimized and greatly promoted.
The syndiotactic polypropylene compound has relatively high crystallization temperature and degree and good hydrophilicity, and can expand the application field of syndiotactic polypropylene.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the embodiment of the invention, the syndiotactic polypropylene resin is polypropylene resin with the syndiotactic degree of more than 90mol percent, which is obtained by polymerizing propylene under the action of metallocene catalyst, and the melt flow rate (230 ℃,2.16 kg) is between 3 and 10g/10 min;
the high density polyethylene has a melt flow rate of about 0.3 to 10g/10min (190 ℃,2.16 kg). Preferably high density polyethylene (HHM) having a melt flow rate of about 0.35g/10min for petrochemical production;
the melt flow rate of the ethylene-vinyl alcohol copolymer is 3-15/10 min (210 ℃,2.16 kg), and the ethylene content is less than or equal to 30 percent. An ethylene-vinyl alcohol copolymer (L101) having an ethylene content of 27wt.% and a melt flow rate of 3.9g/10min, which is preferably available from Colorado, japan;
the melt flow rate (230 ℃,2.16 kg) of the homo-polypropylene is 20-100 g/10min. Preferably, the homopolypropylene Z30S produced by the metallocene petrochemical production has the melt flow rate (230 ℃,2.16 kg) of about 24g/10 min;
the phosphate polypropylene nucleating agent can be selected from LPN-9086 of Pulan polyolefin scientific development (Shanghai) Co., ltd; the antioxidant 1010 and the antioxidant aid 168 are both manufactured by BASF corporation.
The results of the tests for the crystalline properties in the examples according to the invention and in the comparative examples are obtained from the relaxation-resistant DSC214 thermal analyzer and the contact angle test results are obtained from the German Kruss standard contact angle measuring instrument DSA25.
Example 1
Weighing the following raw materials in proportion: 91.1 parts by mass of syndiotactic polypropylene, 6 parts by mass of high density polyethylene (HHM), 2 parts by mass of ethylene-vinyl alcohol copolymer, 0.5 part by mass of homo-polypropylene, 0.2 part by mass of nucleating agent LPN9086, 0.1 part by mass of antioxidant 1010 and 0.1 part by mass of antioxidant 168. The syndiotactic polypropylene, the high-density polyethylene, the ethylene-vinyl alcohol copolymer, the homopolymerized polypropylene, the nucleating agent, the antioxidant 1010 and the antioxidant 168 are premixed, the mixing temperature is 20 ℃, the rotating speed is 200 r/min, and the mixing is carried out for 5 min. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeder, and is subjected to melt extrusion granulation. The process conditions are set as follows: the rotation speed of the screw is 200 r/min, the rotation speed of the feeding machine is 30 r/min, and the temperature of each section of the extruding machine is 170-220 ℃. And (5) drawing strips, watering and granulating.
And (3) performing DSC (differential scanning calorimetry) test on the dried syndiotactic polypropylene composite material, wherein all experiments are performed in a nitrogen atmosphere, the mass of a sample is 5-8mg, and the heating and cooling rates are both 10K/min. The composite was hot pressed into sheets at 190 ℃ and subjected to a water contact angle test. The test results are shown in Table 1.
Example 2
Weighing the following raw materials in proportion: 86.3 parts of syndiotactic polypropylene, 5 parts of ethylene-vinyl alcohol copolymer, 8 parts of homopolymerized polypropylene, 0.1 part of nucleating agent LPN9086, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168. The syndiotactic polypropylene, the ethylene-vinyl alcohol copolymer, the homo-polypropylene, the nucleating agent, the antioxidant 1010 and the antioxidant 168 are premixed, the mixing temperature is 30 ℃, the rotating speed is 300 r/min, and the mixing is carried out for 3 min. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions were set as follows: the rotating speed of the screw is 300 r/min, the rotating speed of the feeding machine is 20 r/min, and the temperature of each section of the extruding machine is 170-220 ℃. And (5) drawing strips, watering and granulating.
And (3) carrying out DSC test on the dried polypropylene composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating rate and the cooling rate are both 10K/min. The composite was hot pressed into sheets at 190 ℃ and subjected to a water contact angle test. The test results are shown in Table 1.
Example 3
Weighing the following raw materials in proportion: 84.0 parts by mass of syndiotactic polypropylene, 7.5 parts by mass of high density polyethylene (HHM), 3 parts by mass of ethylene-vinyl alcohol copolymer, 5 parts by mass of homo-polypropylene, 0.2 part by mass of antioxidant 1010 and 0.3 part by mass of antioxidant 168. The syndiotactic polypropylene, the high-density polyethylene, the ethylene-vinyl alcohol copolymer, the homopolymerized polypropylene, the antioxidant 1010 and the antioxidant 168 are premixed, the mixing temperature is 25 ℃, the rotating speed is 250 r/min, and the mixing is carried out for 4 min. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions were set as follows: the rotation speed of the screw is 150 r/min, the rotation speed of the feeding machine is 25 r/min, and the temperature of each section of the extruding machine is 170-220 ℃. And (5) pulling strips, and carrying out water granulation.
And (3) carrying out DSC test on the dried polypropylene composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating rate and the cooling rate are both 10K/min. The composite was hot pressed into sheets at 190 ℃ and subjected to water contact angle testing. The test results are shown in Table 1.
Example 4
Weighing the following raw materials in proportion: 87.4 parts by mass of syndiotactic polypropylene, 2 parts by mass of high density polyethylene (HHM), 10 parts by mass of ethylene-vinyl alcohol copolymer, 0.2 part by mass of nucleating agent LPN9080, 0.3 part by mass of antioxidant 1010 and 0.1 part by mass of antioxidant 168. The syndiotactic polypropylene, the high-density polyethylene, the ethylene-vinyl alcohol copolymer, the nucleating agent, the antioxidant 1010 and the antioxidant 168 are premixed, the mixing temperature is 23 ℃, the rotating speed is 260 r/min, and the mixing is carried out for 4 min. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions are set as follows: the rotating speed of the screw is 220 r/min, the rotating speed of the feeding machine is 25 r/min, and the temperature of each section of the extruding machine is 170-220 ℃. And (5) pulling strips, and carrying out water granulation.
And (3) carrying out DSC test on the dried polypropylene composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating rate and the cooling rate are both 10K/min. The composite was hot pressed into sheets at 190 ℃ and subjected to a water contact angle test. The test results are shown in Table 1.
Example 5
Weighing the following raw materials in proportion: 80.0 parts by mass of syndiotactic polypropylene, 10 parts by mass of high density polyethylene (HHM), 6.5 parts by mass of an ethylene-propylene alcohol copolymer, 3 parts by mass of homo-polypropylene, 0.1 part by mass of a nucleating agent LPN9080, 0.2 part by mass of an antioxidant 1010 and 0.2 part by mass of an auxiliary antioxidant 168. The syndiotactic polypropylene, the high-density polyethylene, the ethylene-vinyl alcohol copolymer, the homopolymerized polypropylene, the nucleating agent, the antioxidant 1010 and the antioxidant 168 are premixed, the mixing temperature is 28 ℃, the rotating speed is 500 r/min, and the mixing is carried out for 3 min. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeder, and is subjected to melt extrusion granulation. The process conditions were set as follows: the rotating speed of the screw is 290 revolutions per minute, the rotating speed of the feeding machine is 28 revolutions per minute, and the temperature of each section of the extruding machine is 170-220 ℃. And (5) pulling strips, and carrying out water granulation.
And (3) carrying out DSC test on the dried polypropylene composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating rate and the cooling rate are both 10K/min. The composite was hot pressed into sheets at 190 ℃ and subjected to water contact angle testing. The test results are shown in Table 1.
Comparative example 1
Weighing the following raw materials in proportion: 99.7 parts of syndiotactic polypropylene, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 168. Premixing the syndiotactic polypropylene, the antioxidant 1010 and the antioxidant 168 at the mixing temperature of 30 ℃ and the rotation speed of 300 r/min for 3 min. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions are set as follows: the rotating speed of the screw is 300 r/min, the rotating speed of the feeding machine is 30 r/min, and the temperature of each section of the extruding machine is 170-220 ℃. And (5) pulling strips, and carrying out water granulation.
And (3) carrying out DSC test on the dried syndiotactic polypropylene sample, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating rate and the cooling rate are both 10K/min. The composite was hot pressed into sheets at 190 ℃ and subjected to water contact angle testing. The test results are shown in Table 1.
Table examples and comparative examples the thermal properties of the composites obtained
As described above, the present invention can be preferably implemented. The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
High-crystallinity hydrophilic syndiotactic polypropylene composite material and preparation method abstract thereof
The invention discloses a hydrophilic syndiotactic polypropylene composite material with high crystallization temperature and a preparation method thereof. The composite material comprises the following components in parts by weight: 80.0 to 91.1 portions of syndiotactic polypropylene; 0 to 10 portions of polyethylene; 2-10 parts of ethylene-vinyl alcohol copolymer; 0 to 8 portions of homopolymerized polypropylene; 0 to 0.2 percent of nucleating agent; 0.1 to 0.3 percent of antioxidant; 0.1 to 0.3 percent of antioxidant aid. The components are mixed and extruded by a double-screw extruder for granulation to obtain the syndiotactic polypropylene composite material. EVOH has stronger crystallization performance because of containing ethylene chain segments of block copolymerization, and can induce ordered folding of sPP molecular chains, thereby promoting the improvement of sPP crystallization performance. Moreover, EVOH contains a certain proportion of polar groups, so that the composite material can be endowed with better hydrophilic performance. By compounding the EVOH with the effective crystallization promoting components of sPP such as iPP, HDPE and the like, the characteristics of each component are comprehensively utilized, and the crystallization performance of the sPP is expected to be optimized and greatly promoted. The invention not only expands the selection range of the sPP crystallization performance promoter, but also can extend the application field of the sPP.
Claims (8)
1. The hydrophilic syndiotactic polypropylene composite material with high crystallinity is characterized by comprising the following components in parts by weight:
2. the high crystallization temperature hydrophilic syndiotactic polypropylene composite in claim 1, wherein said syndiotactic polypropylene has a melt flow rate of 1-20 g/10min and a degree of syndiotacticity of 80% or more.
3. The high crystallization temperature hydrophilic syndiotactic polypropylene composite in claim 2, wherein said high density polyethylene has a melt flow rate of about 0.5 to 10g/10min, (190 ℃,2.16 kg).
4. The high crystallization temperature hydrophilic syndiotactic polypropylene composite in claim 3, wherein said ethylene-vinyl alcohol copolymer has a melt flow rate of 3-15 g/10min (210 ℃,2.16 kg) and an ethylene content of 50% or less.
5. The hydrophilic syndiotactic polypropylene composite with high crystallization temperature in claim 4, wherein said homopolypropylene has a melt flow rate of 2-30 g/10min, (230 ℃,2.16 kg) and an isotacticity of 95% or more.
6. The high crystallization temperature hydrophilic syndiotactic polypropylene composite in claim 5, wherein said nucleating agent is a phosphate-based polypropylene nucleating agent.
7. The high crystallization temperature hydrophilic syndiotactic polypropylene composite in claim 6, wherein said antioxidant is antioxidant 1010 (pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate); the auxiliary antioxidant is antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite).
8. A method for preparing the high crystallization temperature hydrophilic syndiotactic polypropylene composite in accordance with any one of claims 1-7, comprising the steps of:
(1) Mixing: sequentially adding syndiotactic polypropylene, high-density polyethylene, ethylene-vinyl alcohol copolymer, homo-polypropylene, nucleating agent and the like into a high-speed mixer for premixing, wherein the mixing temperature is 20-30 ℃, the rotating speed is 200-500 r/min, and the mixing time is 3-5 minutes to obtain a premix of a syndiotactic polypropylene compound;
(2) And (3) double-screw extrusion granulation: extruding and granulating the premix obtained in the step (1) by using a parallel co-rotating double-screw extruder with the length-diameter ratio of 40;
the specific process conditions of the twin-screw extrusion granulation are as follows:
extruding and granulating by a parallel co-rotating double-screw extruder with the length-diameter ratio of 40; the rotating speed of the feeder is set to be 20-30 revolutions per minute, and the rotating speed of the screw is 150-500 revolutions per minute; the temperature of each section of the extruder is 170-220 ℃, and the syndiotactic polypropylene compound is obtained.
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| Title |
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| 罗大军等: "PP/PP-g-MAH/EVOH共混物流变和结晶行为研究", 《塑料科技》, no. 10, pages 44 - 47 * |
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