CN110183559B - Production method of polypropylene resin for high-fluidity spun-bonded non-woven fabric - Google Patents
Production method of polypropylene resin for high-fluidity spun-bonded non-woven fabric Download PDFInfo
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- CN110183559B CN110183559B CN201910271318.6A CN201910271318A CN110183559B CN 110183559 B CN110183559 B CN 110183559B CN 201910271318 A CN201910271318 A CN 201910271318A CN 110183559 B CN110183559 B CN 110183559B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
Abstract
The invention discloses a production method of polypropylene resin for high-fluidity spun-bonded non-woven fabric, which comprises the steps of mixing a catalyst system, hydrogen and propylene in a polymerization reactor for polymerization reaction to obtain a first product system with a melt index of 10-15g/10min at the temperature of 230 ℃ and under the load of 2.16kg, mixing the first product system with an additive, extruding and granulating to obtain the polypropylene resin with a melt index of 20-45g/10min at the temperature of 230 ℃ and under the load of 2.16kg and a molecular weight distribution index Mw/Mn of 4-6. It has high melt index, good processing performance and low smell; in the production process, the transition materials are few, the switching period is short, the production rate is high, the molecular weight distribution is narrow, and the tensile strength and the elongation of the fiber are improved; the spun-bonded non-woven fabric processed by the resin has the advantages of low peroxide residue, high cracking rate, high spinning uniformity and stability, strong practicability and wide applicability.
Description
Technical Field
The invention relates to a polypropylene resin, in particular to a production method of a polypropylene resin for high-fluidity spun-bonded non-woven fabric.
Background
Polypropylene is typically produced by polymerizing propylene monomers in the presence of a ziegler-natta catalyst, i.e. a catalyst comprising a titanium halide. These catalysts usually also contain internal electron donors such as phthalates, diethers, etc. The existing production device process mostly adopts a loop process, the process needs pre-contact and pre-polymerization of the catalyst due to the essential requirement of liquid-phase bulk polymerization, and two groups of loop reactors connected in series are generally needed. High-pressure and low-pressure flash separated gas needs to be washed to remove fine powder, steaming and drying tail gas also needs to be washed, only one homopolymerization reactor is needed for producing homopolymerization propylene and random copolymerization polypropylene by a gas phase method, and most polymer powder behind the reactor is treated by a degassing bin one-step method. Therefore, the gas phase method has short process flow, less equipment and simpler flow configuration than the ring tube method. And the gas phase method has more safe production process because the operation conditions such as polymerization pressure, temperature and the like are milder than those of the ring tube method.
Polypropylene has now become one of the most widely used polymers in spunbond nonwovens. Because of its light weight, high strength, good elasticity, abrasion resistance, corrosion resistance, etc., polypropylene nonwoven fabrics are used in a variety of products, such as disposable hygiene articles including diapers, sanitary napkins, training pants, adult incontinence products, hospital gowns, wet hand towels, sanitary garments, and the like.
In order to produce good processability and nonwoven properties in spunbond nonwovens, it is necessary to narrow the molecular weight distribution, which can be achieved thermally or chemically by degradation. Particularly, with the development of differentiation and functionalization of polypropylene fibers, higher requirements are put forward on special resins for spun-bonded non-woven fabrics, such as high melt flow rate, narrow molecular weight distribution, high isotacticity, high elongation at break, low ash and the like, so as to improve fiber spinning speed and reduce processing temperature, and high tensile property can reduce fiber fineness, so that the product is thin and meets the requirements of non-woven fabrics on properties such as hand feeling and strength.
At present, the melt flow index of polypropylene generally used for spun-bonded non-woven fabrics is 20g/10min-45g/10min, and the methods for industrially producing high-fluidity polypropylene mainly comprise a hydrogen regulation method and a direct chemical degradation regulation method.
The hydrogen regulating process is that hydrogen as molecular weight regulator is introduced into the polymerization reactor of polypropylene to react with the active center of catalyst to stop the further growth of polypropylene chain and to make the material resin possess high melt flowability.
The direct chemical degradation regulating method is to add great amount of peroxide into polypropylene base resin for degradation to raise its melt index. Although the polypropylene resin prepared by the method has narrow molecular weight distribution and better fiber forming performance, the use of a large amount of peroxide increases the product cost on one hand, and the residual peroxide can further degrade the polypropylene non-woven fabric and cause the finally obtained polypropylene spun-bonded non-woven fabric to generate taste, so that the skin sensitive people feel uncomfortable and the application of the polypropylene spun-bonded non-woven fabric in certain fields (such as medical treatment and health, food and the like) is limited.
The product quality prepared by the polypropylene resin for domestic high-fluidity spun-bonded non-woven fabric has the problems of large melt index fluctuation, wide molecular weight distribution, high impurity content, serious yarn breaking and doubling phenomenon in production and the like, and can only be applied to low-end products, while most of special resins for high-grade polypropylene fibers (such as fine denier, ultra-fine denier, melt-blown non-woven fabrics and the like) need to be imported, and the imported raw materials are mainly used for producing export products, sanitary protection products, medical and health products and the like with higher quality requirements.
Therefore, there is a need for a method for preparing polypropylene resin for high-fluidity spunbonded nonwoven fabrics, which has the processability of high melt index and narrow molecular weight distribution, and simultaneously maintains excellent mechanical properties and ensures that the resin has uniform and stable fiber forming performance.
The CN103788259B patent discloses a method for directly preparing a propylene polymer with narrow molecular weight distribution by reactor polymerization, which comprises the steps of prepolymerizing propylene at-10 ℃ to 50 ℃ and 0.1 to 10.0MPa in the presence of a ziegler-natta catalyst in gas phase or liquid phase to obtain a propylene prepolymer; in the presence of the resulting propylene prepolymer, homopolymerization of propylene is carried out at 91-110 ℃ under 1.5-5.5MPa in the gas phase or liquid phase; the polymerization reaction time is 0.5-4.0 hours, and the obtained propylene polymer is obtained. The method is a ring pipe type production process of liquid phase bulk polymerization, and has more complex production flow and higher requirements on production conditions.
The CN105143528B patent discloses a new polypropylene fiber and a method for preparing a spunbonded nonwoven fabric made of the same, which uses a specific kind of diether and succinate compounded internal electron donor catalyst and a liquid phase process to prepare a polypropylene precursor first, and then carries out chemical degradation of peroxide. The relative molecular mass distribution Mw/Mn of the polypropylene fiber prepared by the method is in a wide range of 3-12.
The CN1072738C patent discloses a method for preparing polypropylene fiber spinning material, which is mainly characterized in that peroxide and polypropylene resin are melt-extruded by twin screws, and the obtained peroxide concentrated master batch and the polypropylene resin are melt-extruded by the twin screws again to prepare the polypropylene fiber spinning material. The method has higher requirements on the stability of the peroxide master batch, the cost is higher, and the compatibility with polypropylene resin is to be evaluated.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the polypropylene resin for the high-fluidity spunbonded nonwoven fabric, which has high melt index, narrower molecular weight distribution, low odor, excellent mechanical properties, higher tensile strength, higher elongation at break, low ash content and other good fiber forming properties.
In order to achieve the above object, the present invention adopts the following technical solutions:
a production method of polypropylene resin for high-fluidity spun-bonded non-woven fabric comprises the following steps:
s1, mixing the catalyst system, hydrogen and propylene in a polymerization reactor for polymerization reaction to obtain a first product system, wherein the melt index of the first product system is 10-15g/10min at the temperature of 230 ℃ and under the load of 2.16 kg;
and S2, mixing the first product system and additives, extruding and granulating to obtain the polypropylene resin, wherein the melt index of the polypropylene resin is 20-45g/10min under the conditions that the temperature is 230 ℃ and the load is 2.16kg, and the molecular weight distribution index Mw/Mn is 4-6.
The polymerization reaction comprises the following steps:
a1, feeding propylene into a polymerization reactor, establishing the propylene partial pressure to 3.0-3.2MPa,
a2, feeding hydrogen to the polymerization reactor to H2/C3The molar ratio of (A) is 0.01-0.03; injecting a catalyst system into the polymerization reactor;
a3, after the reaction is started, adding propylene to maintain the propylene partial pressure in the polymerization reactor at 3.0-3.2MPa and ensure H2/C3The ratio of Al/Ti to Al/Si, namely, the component proportion is maintained by controlling the feeding amount of each material, the flow is stable, the feeding amounts of the catalyst and propylene are adjusted, and the load of a polymerization reactor is increased to 52t/h on the premise of ensuring the propylene partial pressure;
a4 adjusting H as appropriate2/C3And controlling the melt index of the first product system within the range of 10-15g/10 min.
The barrel temperature of the extruder in the S2 is 210-240 ℃, and the temperature of the granulating water is 40-60 ℃.
In the extrusion granulation in step S2, the contents of the first product system and the additive are as follows in parts by weight:
100 parts of a first product system, 0.05-0.3 part of antioxidant, 0.01-0.04 part of degradation agent and 0.02-0.1 part of acid acceptor;
the degradation agent comprises (2, 5-dimethyl-2, 5-bis (t-butylperoxy)) hexane;
the acid scavenger comprises calcium stearate;
the antioxidant comprises a main antioxidant and an auxiliary antioxidant;
the main antioxidant is a phenol antioxidant and comprises at least one of 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester,
the antioxidant aid is a phosphite antioxidant, and the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.
The catalyst system comprises a carrier, an external electron donor, a cocatalyst, an internal electron donor, a titanium compound containing a titanium-halogen bond, and is preferably a SHAC series catalyst;
the external electron donor is one of alkoxysilane compounds, diisobutyldimethoxysilane, diisopropyldimethoxysilane, isobutylmethyldimethoxysilane, tetraethoxysilane, n-propyltriethoxysilane and cyclohexylmethyldimethoxysilane;
the internal electron donor is one of phthalate ester, di-n-butyl phthalate, diisobutyl phthalate, 9-dimethoxymethylfluorene, 2-diethyl malonic acid di-n-butyl ester, 2-isobutyl diethyl maleate, 3-dimethyl diethyl glutarate and di-n-butyl phthalate ester;
the cocatalyst comprises triethylaluminum;
the carrier comprises magnesium chloride and magnesium ethoxide.
Further, the external electron donor is preferably diisobutyldimethoxysilane, diisopropyldimethoxysilane or n-propyltriethoxysilane.
Furthermore, the molar ratio of the cocatalyst to the external electron donor is calculated by Al and Si, and the ratio of the cocatalyst to the external electron donor is 6-10, preferably 7-9;
furthermore, the molar ratio of the above-mentioned cocatalyst to the catalyst, calculated on the basis of the elements Al and Ti, should be 40-60, preferably 40-50.
The polymerization reactor is a Unipol gas-phase polymerization reactor; the reaction temperature is 65-75 deg.C and the pressure is 2.8-3.3 Mpa.
The cracking rate CE of the polypropylene resin is more than or equal to 90 percent, and the CE is defined by the following formula I:
the improvement of the polypropylene resin during the production process of the spun-bonded non-woven fabric is realized by the maximum box air pressure and the maximum pressure deviation A is kept for t ≥ 168 hoursm5% or less, wherein the improvement is defined by the following formulas II and III:
Am/Bm≥1.1 (II)
ΔAmwhen t is not less than 5 percent and not less than 168h (III)
In the formula, AmMaximum applicable tank air pressure [ MPa ] for the prepared polypropylene resin]，
BmMaximum applicable box air pressure [ MPa ] of polypropylene resin prepared by other methods]。
The invention has the advantages that:
the polypropylene resin for the high-fluidity spun-bonded non-woven fabric has the following advantages:
1. the resin has high melt index, good processing performance, excellent mechanical performance, uniform and stable fiber forming performance and low smell; compared with a liquid-phase bulk method, the preparation method of the gas-phase polymerization for producing the resin has the advantages of stable and simple production, flexible production conversion and no prepolymerization process, and adopts a large Unipol gas-phase fluidized bed reactor to produce the homopolymer, thereby reducing the risk of agglomeration of fine powder in the reactor when the high-melt-index homopolymerization polypropylene resin is produced.
2. The invention combines the advantages of the hydrogen regulation method and the degradation method, adopts the hydrogen regulation method to produce the base resin with the melt index (230 ℃, 2.16kg) of 10-15g/10min, and then adds a small amount of peroxide to degrade the base resin to ensure that the melt index (230 ℃, 2.16kg) of the resin reaches 18-45g/10 min. Compared with a pure hydrogen adjusting method, the production process has the advantages of less transition materials, short switching period, high production rate and narrow molecular weight distribution of products, and the tensile strength and the elongation of the fiber are improved; compared with the chemical degradation method by directly adding a large amount of peroxide, the resin product has lower odor, low yellow index and good appearance, and is particularly suitable for the fields of medical treatment, health care, food and the like.
3. The spun-bonded non-woven fabric processed and prepared by the resin has the advantages of low peroxide residue, high cracking rate, high spinning uniformity and stability, less fluctuation of influencing factors in the spinning process, production of fibers with smaller diameters by increasing the maximum spinning speed, improvement of processability, no influence on mechanical properties such as tensile strength, elongation and the like, and the preparation method is superior to the spun-bonded non-woven fabric processed and produced by the resin prepared by a pure hydrogen blending method and a direct degradation method.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
A production method of polypropylene resin for high-fluidity spun-bonded non-woven fabric comprises the following steps:
s1, mixing the catalyst system, hydrogen and propylene in a Unipol gas phase polymerization reactor for polymerization reaction to obtain a first product system, wherein the melt index of the first product system is 10-15g/10min under the conditions that the temperature is 230 ℃ and the load is 2.16 kg.
The catalyst system adopts SHACTM201, comprising titanium tetrachloride, magnesium chloride as a carrier, n-propyltriethoxysilane as an external electron donor, triethyl aluminum as a cocatalyst and phthalate as an internal electron donor; wherein, the molar ratio of the cocatalyst to the external electron donor is 6-10; the molar ratio of cocatalyst to catalyst, i.e. the element Al/Ti, is between 40 and 60.
The polymerization reaction is specifically operated as follows:
a1, feeding propylene into a Unipol gas-phase polymerization reactor, establishing the propylene partial pressure to 3.0-3.2MPa,
a2, feeding hydrogen into the reactor to H2/C3The molar ratio of the hydrogen to the organic solvent is 0.01-0.03, and the adding amount of the hydrogen is 4-7 kg/h; injecting a catalyst system into the polymerization reactor;
a3, after the reaction, propylene was addedMaintaining the propylene partial pressure in the polymerization reactor at 3.0-3.2MPa to ensure that H is in the range of2/C3The ratio of Al/Ti to Al/Si, namely, the component proportion is maintained by controlling the feeding amount of each material, the flow is stable, the flow of the catalyst carrier is 80kg/h, the feeding amount of propylene is 57000-59000kg/h, and the load of a polymerization reactor is increased to 52t/h on the premise of ensuring the partial pressure of the propylene;
a4 adjusting H as appropriate2/C3And controlling the melt index of the first product system within the range of 10-15g/10 min.
S2, mixing 100 parts of the first product system and 0.01-0.04 part of degrading agent according to mass fraction, extruding and granulating by an extruder to obtain the polypropylene resin, wherein the melt index of the polypropylene resin is 20-45g/10min under the conditions of 230 ℃ and 2.16kg of load, and the molecular weight distribution index Mw/Mn is 4-6.
The degradation agent is (2, 5-dimethyl-2, 5-bis (tert-butylperoxy)) hexane.
Relevant process parameters for examples 1-2 and comparative examples 1-3 in the polymerization reaction are given in table 1 below:
examples 3 to 10 were conducted by subjecting the first product systems of examples 1 to 2 and comparative examples 1 to 3 to extrusion granulation in step S2 in the presence of the following additives, adjusting the extruder parameters based on the results of the granule analysis, and controlling the extruder barrel temperature at 210 ℃ and the pellet water temperature at 40 ℃ to 60 ℃; the additive comprises the following components:
the main antioxidant 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, the auxiliary antioxidant (tris [2, 4-di-tert-butylphenyl ] phosphite 168), the degradant (2, 5-dimethyl-2, 5-bis (tert-butylperoxy)) hexane, the acid scavenger calcium stearate, the amounts of the above additives are shown in table 2 below:
the performance tests were performed according to the following criteria:
the sample melt flow rate (MFR value) was measured according to GBT 3682-2000 standard under 230 ℃ C.under a load of 2.16 kg.
Tensile properties were tested according to ISO 527-1-2012 standard.
Molecular mass distribution index Mw/Mn, the molecular weight of the sample was measured using Gel Permeation Chromatography (GPC), the sample was dissolved in 1,2, 4-trichlorobenzene, where trichlorobenzene is the mobile phase at a temperature of 150 ℃, the resulting solution was injected into gel permeation chromatography and analyzed under conditions well known in the polymer industry.
Odor testing, performed as standard for the component odor test (mass vehicle standard) of the interior of the PV3900(2000) vehicle.
And (3) testing the cracking rate, namely testing the melt flow rate of the sample, cooling and crushing polypropylene granules in liquid nitrogen when preparing the sample added with 0.5% of BHT antioxidant, fully and uniformly mixing the crushed polypropylene granules with the BHT antioxidant, and then testing the MFR value.
The polypropylene resins prepared in examples 3 to 6 and comparative examples 4 to 7 were analyzed by the above-mentioned test methods for melt index, tensile break stress, tensile break nominal strain and molecular mass distribution Mw/Mn, and the test results are shown in Table 3 below.
Remarking: odor grade, 1 not perceptible; 2 perceptible, non-obtrusive; 3 is clearly perceptible but not too obstructive; 4 is obstructive; 5 are greatly hampered; 6 are intolerable.
As can be seen from the above table 3 and the above description, the polypropylene resin special for high-fluidity spun-bonded non-woven fabric prepared by the production method provided by the invention achieves the following effects:
examples 3-6 have high melt index, narrow molecular weight distribution, good mechanical properties, high tensile strength and elongation at break, good fiber forming properties.
The propylene feeding amount of the polymerization reactions of examples 3 to 6 and comparative examples 7 to 8 can be found that as the hydrogen concentration increases, the polymerization device needs more propylene to stabilize the reaction, which not only brings about the hidden trouble of production safety, but also has a certain risk of heat exchange amount carried away by propylene during production.
Furthermore, the molecular mass distribution indexes of comparative examples 7-8 are also significantly higher than those of examples 3-6, and the tensile properties are all reduced from those of examples 3-6, indicating that the spinning performance of the product prepared by the equilibrium method of hydrogen-mediated degradation is better than that of the pure hydrogen-mediated method.
The cracking rates of examples 3-6 were significantly higher than those of comparative examples 9-10 and the cracking rates of the comparative examples were all below 90%, indirectly indicating that the residual peroxide in the comparative examples was high and the odor was relatively high, consistent with the odor test results.
Preparation of polypropylene fiber spunbonded nonwoven fabric:
spunbond nonwovens were produced using the above-described raw material polypropylene of examples 3, 7 and 9 on a 1-meter wide Reicofilt 4 line with a single die having a cut out of about 7000 holes per meter length, the diameter of the holes being 0.6 mm. The yield per well was set to 0.41 g/well/min. The line speed was kept at 250 m/min. The nonwoven fabric produced by the process has a fabric weight of 12g/m2The nonwoven fabric was thermally bonded using an embossing roll.
Table 4 below is data on the filament fineness, processability, and mechanical properties of the nonwoven fabrics manufactured by processing the raw materials of example 3, comparative example 4 (example 7), and comparative example 6 (example 9).
Wherein the average fiber diameter in the fabric is determined by measuring 20 randomly selected fiber diameters d using an optical microscope. The filament titer is calculated from the average fiber diameter by the following relationship: d ═ pi D2/4×L×ρ×10-6(ii) a Mechanical properties of the web the tensile strength and elongation of the spunbond nonwoven were measured according to ISO 9073-3:1989 standard.
As can be seen from table 4 above, the polypropylene resin spunbonded nonwoven fabric prepared by the production method provided by the invention achieves the following effects:
example 3 was able to run at a maximum box pressure of 9900MPa, at which the filament titer was only 1.24 denier, whereas comparative example 4 (pure hydrogen conditioning), at which the filament titer was 1.45 denier, was able to run at a maximum box pressure of 8100MPa, at which the deviation of the maximum pressure was also observed to be within 16% (t.ltoreq.300 h), much higher than example 3, the spinning stability was significantly worse, the drawability was also better, and the spinning speed was improved.
Further, although the filament fineness of example 3 was close to that of comparative example 6, which is 1.26 denier, comparative example 6 was only able to operate at a maximum box pressure of 8500Pa (direct degradation method), and the deviation retention of the maximum pressure of comparative example 6 was much lower than that of example 3 (hydrogen addition degradation method), the residue of peroxide was too high to cause poor spinning stability, and the maximum tensile strength was also slightly lower than that of example 3.
In summary, the results show that nonwovens spun-bonded with the polypropylene resins prepared in accordance with the present invention (i.e., polypropylenes characterized by narrower molecular weight distributions than those used in spun-bonded polypropylenes by the hydrogen-blending process, polypropylenes having higher splitting efficiencies and less peroxide residue than those used in spun-bonded polypropylenes by the direct degradation process) have advantages in processability and mechanical properties.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (7)
1. A production method of polypropylene resin for high-fluidity spun-bonded non-woven fabric is characterized by comprising the following steps:
s1, mixing the catalyst system, hydrogen and propylene in a polymerization reactor for polymerization reaction to obtain a first product system, wherein the melt index of the first product system is 10-15g/10min at the temperature of 230 ℃ and under the load of 2.16 kg;
s2, mixing the first product system with additives, and extruding and granulating by an extruder to obtain the polypropylene resin, wherein the polypropylene resin has a melt index of 20-45g/10min under the conditions of 230 ℃ and 2.16kg of load, and the molecular weight distribution index Mw/Mn = 4-6;
the polymerization reaction in the step S1 includes the following steps:
a1, feeding propylene into a polymerization reactor, establishing the propylene partial pressure to 3.0-3.2MPa,
a2, feeding hydrogen to the polymerization reactor to H2/C3After the molar ratio of (a) to (b) is 0.01 to 0.03, injecting a catalyst system into the polymerization reactor;
a3, after the reaction is started, adding propylene to keep the propylene partial pressure in a polymerization reactor at 3.0-3.2MPa, and maintaining the component ratio by controlling the feeding amount of each material; on the premise of ensuring the partial pressure of propylene, the load of a polymerization reactor is increased to 52 t/h;
a4, adjustment H2/C3A first product system with the melt index of 10-15g/10min is produced;
the component contents of the first product system and the additive in the step S2 are calculated by the following parts by weight:
100 parts of a first product system, 0.05-0.3 part of antioxidant, 0.01-0.04 part of degradation agent and 0.02-0.1 part of acid acceptor;
the degradation agent comprises (2, 5-dimethyl-2, 5-bis (t-butylperoxy)) hexane;
the acid scavenger comprises calcium stearate;
the antioxidant comprises a main antioxidant and an auxiliary antioxidant;
the main antioxidant is a phenol antioxidant and comprises at least one of 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene and beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester,
the antioxidant aid is a phosphite antioxidant, and the phosphite antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite;
the polymerization reactor is a Unipol gas-phase polymerization reactor; the reaction temperature is 65-75 deg.C and the pressure is 2.8-3.3 Mpa.
2. The method for producing the polypropylene resin for the high-fluidity spunbonded nonwoven fabric according to claim 1, wherein the catalyst system comprises a carrier, an external electron donor, a cocatalyst, an internal electron donor, a titanium compound containing a titanium-halogen bond;
the external electron donor is one of diisobutyldimethoxysilane, diisopropyldimethoxysilane, isobutylmethyldimethoxysilane, tetraethoxysilane, n-propyltriethoxysilane and cyclohexylmethyldimethoxysilane;
the internal electron donor is one of di-n-butyl phthalate, diisobutyl phthalate, 9-dimethoxymethylfluorene, 2-diethyl malonic acid di-n-butyl ester, 2-isobutyl maleic acid diethyl ester, 3-dimethyl glutaric acid diethyl ester and di-n-butyl phthalate ester;
the cocatalyst comprises triethylaluminum;
the carrier comprises magnesium chloride and magnesium ethoxide.
3. The method for producing polypropylene resin for high fluidity spun-bonded nonwoven fabric according to claim 2, wherein the molar ratio of the cocatalyst to the external electron donor is 6-10 in terms of Al and Si.
4. The method for producing a polypropylene resin for a high flow spunbonded nonwoven fabric according to claim 2, wherein the molar ratio of the cocatalyst to the catalyst is 40 to 600 in terms of the elements Al and Ti.
5. The process for producing a polypropylene resin for a high fluidity spunbonded nonwoven fabric according to claim 1, wherein the barrel temperature of the extruder in S2 is 210 ℃ and 240 ℃ and the temperature of the granulating water is 40 ℃ to 60 ℃.
6. The method for producing polypropylene resin for high-fluidity spunbonded nonwoven fabrics according to claim 1, wherein the polypropylene resin has a cracking rate CE ≥ 90%, and the CE is defined by the following formula I:
the polypropylene pellets without residual peroxide effect were polypropylene pellets with 0.5% BHT antioxidant added.
7. The method of claim 1, wherein the polypropylene resin is used for improving the production period of the spunbonded nonwoven fabric by maintaining the maximum pressure deviation Δ A under the maximum tank air pressure for t ≧ 168 hoursm5% or less, wherein the improvement is defined by the following formulas II and III:
Am/Bm≥1.1 (II)
ΔAmwhen t is not less than 5 percent and not less than 168h (III)
In the formula, AmMaximum applicable tank air pressure [ MPa ] for the prepared polypropylene resin]，
BmMaximum applicable box air pressure [ MPa ] of polypropylene resin prepared by other methods]。
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| CN111499978A (en) * | 2020-05-28 | 2020-08-07 | 徐州海天石化有限公司 | High-melt-index PP powder material capable of being used for producing melt-blown material and preparation method of polypropylene melt-blown material |
| CN112281301A (en) * | 2020-10-15 | 2021-01-29 | 青岛大学 | High-elasticity recovery melt-blown non-woven fabric and preparation method thereof |
| CN112281313A (en) * | 2020-10-15 | 2021-01-29 | 青岛大学 | High-elasticity recovery spun-bonded non-woven fabric and preparation method thereof |
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| CN112961439B (en) * | 2021-02-10 | 2022-09-30 | 中国神华煤制油化工有限公司 | Polypropylene resin composition, preparation method and application thereof |
| CN113388203B (en) * | 2021-06-30 | 2022-07-05 | 中国石油化工股份有限公司 | Special material for radiation-resistant bactericidal polypropylene spun-bonded non-woven fabric and preparation method thereof |
| CN113968923B (en) * | 2021-11-23 | 2023-04-07 | 东华能源(宁波)新材料有限公司 | Preparation method of polypropylene resin powder, polypropylene resin particle and polypropylene resin non-woven fabric |
| CN115302895A (en) * | 2022-07-11 | 2022-11-08 | 张家港飞腾复合新材料股份有限公司 | Light composite board with stable application and production process thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788259A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Polypropylene with narrow distribution of molecular weight |
| CN105143528A (en) * | 2012-07-06 | 2015-12-09 | 巴塞尔聚烯烃意大利有限公司 | Polypropylene fiber |
| CN105294894A (en) * | 2015-11-14 | 2016-02-03 | 新疆独山子天利高新技术股份有限公司 | Ultrahigh-fluidity narrow-distribution polypropylene and preparation method thereof |
| CN105733093A (en) * | 2016-03-28 | 2016-07-06 | 中国石油化工股份有限公司 | Special high-flowability resin for polypropylene fibers and preparation method thereof |
| CN106432558A (en) * | 2015-08-05 | 2017-02-22 | 中国石油天然气股份有限公司 | Polypropylene resin special for non-woven fabrics and synthetic method of polypropylene resin |
| CN107629155A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | A kind of polypropylene and its preparation method and application |
| CN109354770A (en) * | 2018-10-25 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of non-woven cloth acrylic resin and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2070956A1 (en) * | 2007-12-14 | 2009-06-17 | Total Petrochemicals Research Feluy | Process for the production of a bimodal polypropylene having low ash content |
| EP2093315A1 (en) * | 2008-02-22 | 2009-08-26 | Total Petrochemicals Research Feluy | Fibres and nonwoven prepared from polypropylene having a large dispersity index |
-
2019
- 2019-04-04 CN CN201910271318.6A patent/CN110183559B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105143528A (en) * | 2012-07-06 | 2015-12-09 | 巴塞尔聚烯烃意大利有限公司 | Polypropylene fiber |
| CN103788259A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Polypropylene with narrow distribution of molecular weight |
| CN106432558A (en) * | 2015-08-05 | 2017-02-22 | 中国石油天然气股份有限公司 | Polypropylene resin special for non-woven fabrics and synthetic method of polypropylene resin |
| CN105294894A (en) * | 2015-11-14 | 2016-02-03 | 新疆独山子天利高新技术股份有限公司 | Ultrahigh-fluidity narrow-distribution polypropylene and preparation method thereof |
| CN105733093A (en) * | 2016-03-28 | 2016-07-06 | 中国石油化工股份有限公司 | Special high-flowability resin for polypropylene fibers and preparation method thereof |
| CN107629155A (en) * | 2016-07-18 | 2018-01-26 | 中国石油化工股份有限公司 | A kind of polypropylene and its preparation method and application |
| CN109354770A (en) * | 2018-10-25 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of non-woven cloth acrylic resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 无纺布专用聚丙烯树脂PPH-Y35的开发;曹圣贤;《河南化工》;20160815(第8期);第25-29页 * |
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