CN110183559A - A kind of production method of high fluidity spun-bonded non-woven acrylic resin - Google Patents
A kind of production method of high fluidity spun-bonded non-woven acrylic resin Download PDFInfo
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- CN110183559A CN110183559A CN201910271318.6A CN201910271318A CN110183559A CN 110183559 A CN110183559 A CN 110183559A CN 201910271318 A CN201910271318 A CN 201910271318A CN 110183559 A CN110183559 A CN 110183559A
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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
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Abstract
The invention discloses a kind of production methods of high fluidity spun-bonded non-woven acrylic resin, polymerization reaction is carried out by the way that catalyst system, hydrogen and propylene to be mixed in polymer reactor, the first product system that melt index under the conditions of 230 DEG C, load 2.16kg is 10-15g/10min is made, it is mixed again with additive, melt index through extrusion granulation under the conditions of 230 DEG C, load 2.16kg is 20-45g/10min, the obtained acrylic resin of molecular weight distributing index Mw/Mn=4-6., with high fusion index, processing performance is good for it, and smell is low；Transition Materials are few in production process, and switching cycle is short, and throughput rate is high, and molecular weight distribution is relatively narrow, improves tensile strength of fiber and elongation；The spun-bonded non-woven that this resin is processed into, peroxide residual quantity is low, and cleavage rate is high, and spinning stable homogeneous is higher, has very strong practicability and wide applicability.
Description
Technical field
The present invention relates to a kind of acrylic resins, and in particular to a kind of high fluidity spun-bonded non-woven acrylic resin
Production method.
Background technique
Polypropylene is usually gathered in the presence of Ziegler-Natta catalyst is the catalyst containing halogenated titanium by propylene monomer
It closes and manufactures.These catalyst usually also contain internal electron donor, such as phthalic acid ester, diether etc..Existing production dress
It sets technique and mostly uses endless tube class technique, for this kind of technique due to the essential requirement of liquid-phase bulk polymerization, catalyst requires pre-contact
And prepolymerization, and generally require two groups of concatenated annular-pipe reactors.The flash separation gas of high and low pressure needs to wash except thin
Powder, decatize, drying tail gas be also required to washing process, and vapor phase method production homo-polypropylene and atactic copolymerized polypropene only need one
Platform homopolymerization device, the polymer powders after reactor mostly use greatly degassing cabin one-step method to handle.Thus gas-phase process process
Short, equipment number is few, and process configuration is simpler than endless tube method.And vapor phase method is because the operating conditions such as polymerization pressure and temperature all compare
Endless tube method mitigates, and production technology is safer.
Polypropylene has become one of most popular polymer in spun-bonded non-woven at present.Since it has quality
Gently, the advantages that strength is high, elasticity is good, wear-resisting, corrosion-resistant, polypropylene non-woven fabric is used for various products, for example including diaper, health
Disposable hygienic article including towel, training pants, adult incontinence products, hospital work clothes, wet towel, cleaner's clothing etc..
In order to generate good processing performance and non-woven fleece property in spun-bonded non-woven, need to become molecular weight distribution
Narrow, this can be realized by degrading with heat or chemical mode.Development differential especially with polypropylene fibre, functionalization,
To spun-bonded non-woven resin dedicated, more stringent requirements are proposed, such as has high melt flow rate (MFR), and Narrow Molecular Weight Distribution is high
Isotacticity, high elongation at tear, low ash point etc. reduces processing temperature to improve Fiber spinning speeds, and high tensile property then may be used
To reduce fibre number, product is thin, meets non-woven fabrics to performance requirements such as feel, intensity.
Currently, the polyacrylic melt flow index commonly used in spun-bonded non-woven is 20g/10min-45g/10min,
And the method for high-flowability polypropylene mainly has hydrogen to adjust method and direct chemical degradation adjusting method in industrial production.
Hydrogen-regulating method is to be passed through polyacrylic in polyacrylic polymerization process using hydrogen as molecular weight regulator
Polymer reactor, hydrogen are reacted with catalyst active center, the further growth of polypropylene chains are terminated, so that material resin be made to have
Having the shortcomings that higher melt flowability, this method is used alone is that Transition Materials are more in production process, and switching cycle is long, raw
It is low to produce rate, in the process of spun-bonded non-woven, phenomena such as being easy to produce fracture of wire, influences processing efficiency, and
Product molecular weight distribution is wider, is unfavorable for improving the intensity of fiber.
Direct chemical degradation adjusts method, is during extruding pelletization, into polypropylene base resin, directly addition is a large amount of
Peroxide degrade, to improve its melt index.Although the molecular weight distribution of acrylic resin made from this method is relatively narrow,
With preferable fibre-forming performance, but the cost that will increase product using one side of a large amount of peroxide, it is on the other hand remaining
Peroxide may make polypropylene non-woven fabric further degrade, and finally obtained PP spunbonded nonwovens is made to generate taste
Road makes skin sensitivity crowd generate uncomfortable and limit it in the application of certain fields (such as health care, food field).
There are melting means fluctuations for product quality prepared by domestic high fluidity spun-bonded non-woven acrylic resin greatly,
Molecular weight distribution is wide, and impurity content is higher, and fracture of wire and the problems such as serious doubling phenomena when production can be only applied to low-end product
In, and high-end polypropylene fibre (such as fine-denier, super fine denier and melt spraying non-woven fabrics) resin dedicated overwhelming majority needs import, these into
Mouth raw material is mainly for the production of exported product and the higher hygienic protection articles of quality requirements and medical and hygiene article etc..
Therefore, it is badly in need of wanting a kind of method preparation high fluidity spun-bonded non-woven acrylic resin, there is high melting to refer to
While several and Narrow Molecular Weight Distribution processing performance, moreover it is possible to keep excellent mechanical performance, it is ensured that resin has stable homogeneous
Fibre-forming performance.
A kind of reactor polymerization of CN103788259B patent disclosure directly prepares molecular weight narrow ditribution acrylic polymers
Method, the method is in the presence of Ziegler-Natta catalyst, in gas phase or liquid phase, by propylene at -10 DEG C to 50 DEG C,
Prepolymerization is carried out under 0.1-10.0MPa, obtains propylene pre-polymer；In the presence of obtained propylene pre-polymer, in 91-110 DEG C,
In 1.5-5.5MPa, in gas phase or liquid phase, the homopolymerization reaction of propylene is carried out；It polymerization reaction time 0.5-4.0 hours, obtains
The acrylic polymers arrived.Such method is the endless tube class production technology of liquid-phase bulk polymerization, and production procedure is complex, produces item
Part is more demanding.
A kind of new polypropylene fibre of CN105143528B patent disclosure and thus the spunbonded nonwoven of fiber manufacture is knitted
The preparation method of object, the method internal electron donor catalyst and liquid phase work compound using particular kind of diether and succinate
Skill first prepares polypropylene precursor, then carries out the chemical degradation of peroxide.The average molecular of polypropylene fibre made from the method
Mass Distribution Mw/Mn range is between 3-12, wider range.
A kind of method for preparing material for production of polypropylene fibers of CN1072738C patent disclosure, is mainly characterized by peroxide
Through twin-screw melting extrusion, obtained peroxide concentration master batch and acrylic resin passes through double again for compound and acrylic resin
Material for production of polypropylene fibers is made in screw rod melting extrusion.This method has higher requirements to the stability of peroxide master batch, and cost
It is higher, also have with the compatibility of acrylic resin to be assessed.
Summary of the invention
To solve the deficiencies in the prior art, point that the purpose of the present invention is to provide a kind of with high fusion index, relatively narrow
Son amount distribution, smell is low, and keeps excellent mechanical property, and tensile strength with higher and elongation at break, ash content are low etc.
The high fluidity spun-bonded non-woven acrylic resin of good fibre-forming performance.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of production method of high fluidity spun-bonded non-woven acrylic resin, comprising the following steps:
S1, it catalyst system, hydrogen and propylene is mixed in polymer reactor carries out polymerization reaction, the first product is made
System, melt index under the conditions of 230 DEG C of temperature, load 2.16kg are 10-15g/10min；
S2, acrylic resin will be obtained after the first product system and additive mixing extrusion granulation, 230 DEG C of temperature,
Melt index under the conditions of load 2.16kg is 20-45g/10min, molecular weight distributing index Mw/Mn=4-6.
Above-mentioned polymerization reaction, comprising the following steps:
A1, into polymer reactor into propylene, establish partial pressure of propylene to 3.0-3.2MPa,
A2, into polymer reactor into hydrogen to H2/C3Molar ratio be 0.01-0.03；It injects and is catalyzed to polymer reactor
Agent system；
After A3, reaction start, it is 3.0-3.2MPa that addition propylene, which keeps polymer reactor inner propene partial pressure, it is ensured that H2/C3、
The ratio of Al/Ti, Al/Si maintain component ratio, and flow trim by controlling each material inlet amount, adjust catalyst
With propylene feed amount, under the premise of guaranteeing partial pressure of propylene, polymer reactor load is improved to 52t/h；
A4, appropriate adjustment H2/C3, the melt index of the first product system is controlled within the scope of 10-15g/10min.
210-240 DEG C of the barrel temperature of extruder in above-mentioned S2,40-60 DEG C of pelletizing coolant-temperature gage.
Extrusion granulation in above-mentioned steps S2, the constituent content of the first product system and additive, come by parts by weight in terms of:
First 100 parts of product system, 0.05-0.3 parts of antioxidant, 0.01-0.04 parts of degradation agent, acid absorbent 0.02-0.1
Part；
The degradation agent includes (2,5- dimethyl -2,5- bis(t-butylperoxy)) hexane；
The acid absorbent includes calcium stearate；
The antioxidant includes primary antioxidant and aid anti-oxidants；
The primary antioxidant is phenolic antioxidant, including 1,3,5- trimethyls -2,4, and (3, the 5- di-t-butyl -4- hydroxyls of 6- tri-
Base benzyl) benzene, at least one of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester,
The aid anti-oxidants are phosphite ester antioxidant, including phosphite ester antioxidant is three (2,4- di-t-butyls
Phenyl) phosphite ester.
Above-mentioned catalyst system including carrier, external electron donor, co-catalyst, internal electron donor, contains titanium-halogen key
Titanium compound, preferably SHAC catalyst series；
The external electron donor is alkoxy silane compound, second, isobutyl dimethoxy silane, diisopropyl diformazan
Oxysilane, isobutyl methyl dimethoxysilane, tetraethoxysilane, n-propyl triethoxysilane, cyclohexylmethyl two
One of methoxy silane；
The internal electron donor is O-phthalic base acid esters, phthalic acid di-n-butyl ester, two isobutyl of phthalic acid
Base ester, 9,9- dimethoxy methyl fluorenes, 2,2- diethyl malonic acid di-n-butyl, 2- isobutyl group diethyl maleate, 3,3- diformazan
One of base ethyl glutarate, di-n-butyl phthalate ester；
The co-catalyst includes triethyl aluminum；
The carrier includes magnesium chloride, magnesium ethylate.
Further, above-mentioned external electron donor, preferably second, isobutyl dimethoxy silane, diisopropyl dimethoxy silicon
Alkane, n-propyl triethoxysilane.
Further, the molar ratio element al and Si of above-mentioned co-catalyst and external electron donor are counted, and the two ratio is 6-
10, preferably 7-9；
Further, the molar ratio element al and Ti of above-mentioned co-catalyst and catalyst are counted, and the two ratio should be 40-
60, preferably 40-50.
Above-mentioned polymer reactor is Unipol gas-phase polymerization reactor；Reaction temperature is 65-75 DEG C, pressure 2.8-
3.3Mpa。
Cleavage rate CE >=90% of above-mentioned acrylic resin, CE are limited by following formula I:
Above-mentioned acrylic resin is applied to the improvement during the production and processing of spun-bonded non-woven, by maximum cabinet air pressure
Power and the holding maximum pressure deviation A in t >=168 hourm≤ 5% indicates the stability of fibre spinning, wherein improve by with
Lower formula II and formula III is limited:
Am/Bm≥1.1 (II)
ΔAm≤ 5% works as t >=168h (III)
In formula, AmFor the maximum applicable cabinet air pressure [MPa] of acrylic resin of preparation,
BmFor the maximum applicable cabinet air pressure [MPa] of acrylic resin of other methods preparation.
The invention has the beneficial effects that:
A kind of high fluidity spun-bonded non-woven acrylic resin of the invention, has the advantage that
1, the resin has high fusion index, and processing performance is good, and is able to maintain excellent mechanical performance, has uniform steady
Fixed fibre-forming performance, smell are low；The preparation method of the gas-phase polymerization of the resin is produced compared with liquid phase noumenal method, produces and stablizes letter
It is single, it changes the line of production flexibly, there is no pre-polymerization process, but a big Unipol gas-phase fluidized-bed reactor is used to produce homopolymer, drop
It is low when producing high fusion index homopolypropylene resin, risk of the fine powder in reactor inner caking.
2, the present invention combines the advantages of hydrogen-regulating method and edman degradation Edman, produces melt index (230 DEG C, 2.16kg) using hydrogen-regulating method
For the base resin of 10-15g/10min, then made by the way that a small amount of peroxide degradation is added the melt index of resin (230 DEG C,
2.16kg) reach 18-45g/10min.Compared with pure hydrogen-regulating method, Transition Materials are few in production process, and switching cycle is short, throughput rate
Height, and product molecular weight distribution is relatively narrow, improves tensile strength of fiber and elongation；Be directly added into a large amount of peroxide
Chemical degradation method is compared, naval stores it is odor profiles lower, yellow colour index is also low, organoleptic good, be particularly suitable for health care,
In terms of the fields such as food.
3, the spun-bonded non-woven that this resin is processed into, peroxide residual quantity is low, and cleavage rate is high, spinning stable homogeneous
Property it is higher, the influence factor fluctuation by spinning process is less, the fiber of smaller diameter is produced by improving maximum spinning speed,
Improve processability, but the mechanical performances such as tensile strength and elongation remain to it is unaffected, be better than pure hydrogen-regulating method and direct edman degradation Edman
Prepare the spun-bonded non-woven of resin processing.
Specific embodiment
Below in conjunction with detailed description of the invention by specific embodiments.
A kind of production method of high fluidity spun-bonded non-woven acrylic resin, comprising the following steps:
S1, it catalyst system, hydrogen and propylene is mixed in Unipol gas-phase polymerization reactor carries out polymerization reaction, make
The first product system is obtained, melt index under the conditions of 230 DEG C of temperature, load 2.16kg is 10-15g/10min.
Catalyst system selects SHACTM201, including titanium tetrachloride, carrier magnesium chloride, three ethoxy of external electron donor n-propyl
Base silane, co-catalyst triethyl aluminum, internal electron donor O-phthalic base acid esters；Wherein, co-catalyst and external electron donor
Molar ratio, i.e. element al/Si=6-10；The molar ratio of co-catalyst and catalyst, i.e. element al/Ti=40-60.
The concrete operations of polymerization reaction are as follows:
A1, into Unipol gas-phase polymerization reactor into propylene, establish partial pressure of propylene to 3.0-3.2MPa,
A2, into reactor into hydrogen to H2/C3Molar ratio be 0.01-0.03, added hydrogen 4-7kg/h；Xiang Ju
Close reactor injecting catalyst system；
After A3, reaction start, it is 3.0-3.2MPa that addition propylene, which keeps polymer reactor inner propene partial pressure, it is ensured that H2/C3、
The ratio of Al/Ti, Al/Si maintain component ratio, and flow trim, catalyst carrier by controlling each material inlet amount
Flow is 80kg/h, and propylene feed amount is 57000-59000kg/h, under the premise of guaranteeing partial pressure of propylene, improves polymer reactor
Load is to 52t/h；
A4, appropriate adjustment H2/C3, the melt index of the first product system is controlled within the scope of 10-15g/10min.
S2, ratio based on mass fraction, after 100 part of first product system and 0.01-0.04 parts of degradation agents are mixed, through squeezing
Acrylic resin is obtained after press extrusion granulation, melt index under the conditions of 230 DEG C of temperature, load 2.16kg is 20-
45g/10min, molecular weight distributing index Mw/Mn=4-6.
Degradation agent is (2,5- dimethyl -2,5- bis(t-butylperoxy)) hexane.
The related process parameters of embodiment 1-2 and comparative example 1-3 in the polymerization, see the table below 1:
Embodiment 3-10 is in the presence of following additive, to the first product system of embodiment 1-2 and comparative example 1-3
The extrusion granulation for carrying out step S2 is analyzed according to pellet as a result, adjustment extruder parameter, controls extruder barrel temperature 210-
240 DEG C, 40-60 DEG C of pelletizing coolant-temperature gage；The each component ingredient of additive, is respectively as follows:
Primary antioxidant 1,3,5- trimethyl -2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyl) benzene, aid anti-oxidants (three
[2.4- di-tert-butyl-phenyl] phosphite ester 168), degradation agent (2,5- dimethyl -2,5- bis(t-butylperoxy)) hexane is inhaled
Sour agent calcium stearate, the amount of above-mentioned additive see the table below 2:
Properties test is carried out by following standard:
Sample melt flow rate (MFR) (MFR value) is carried out by GBT 3682-2000 standard, and test condition is 230 DEG C,
2.16kg loading.
Tensile property test, is carried out by ISO 527-1-2012 standard.
Molecular vibrational temperature index M w/Mn, using the molecular weight of gel permeation chromatography (GPC) measurement sample, by sample
It is dissolved in 1,2,4- trichloro-benzenes, wherein trichloro-benzenes is mobile phase, and temperature is 150 DEG C, and acquired solution is injected into gel infiltration
It is analyzed in chromatography and under conditions well-known in the polymer industry.
Smell test, by PV3900 (2000) automotive interior component Odor Examination (Volkswagen's standard) standard into
Row.
Cleavage rate test is carried out by the testing standard of sample melt flow rate (MFR), and 0.5%BHT antioxidant is added in preparation
Sample when, first by polypropylene granules in liquid nitrogen cooling crush, be sufficiently mixed with BHT antioxidant uniformly carry out MFR again later
Value test.
The melt index of the acrylic resin according to the above method, prepared in test analysis embodiment 3-6 and comparative example 4-7,
Tensile break stress, tension failure norminal strain and molecular vibrational temperature Mw/Mn, test result see the table below 3.
Remarks: oder levels, 1 cannot experience；2 can experience, unobstructive；3 be can obviously experiencing but do not have
There is too big obstruction；4 have obstruction；5 by larger obstruction；6 is insufferable.
From upper table 3 and above description as it can be seen that the high fluidity spun-bonded non-woven of production method provided by the invention preparation
Polypropylene dedicated resin has reached following effect:
Embodiment 3-6 has high fusion index, Narrow Molecular Weight Distribution, keeps excellent mechanical property, drawing with higher
Stretch intensity and elongation at break, good fibre-forming performance.
The polymerization reaction propylene feed amount of embodiment 3-6 and comparative example 7-8 it can be found that with density of hydrogen rising,
Polyplant needs more propylene to stablize reaction, not only brings the hidden danger of production safety, so that passing through propylene band when production
There is also certain risks for the heat exchange amount walked.
Moreover, the molecular vibrational temperature index of comparative example 7-8 is also apparently higher than embodiment 3-6, tensile property is all than implementing
Example 3-6 is declined, and illustrates that the spinning properties for adding the balancing method of degradation that product is made by hydrogen tune will be better than pure hydrogen-regulating method.
The cleavage rate of example 3-6 is obviously much higher than comparative example 9-10 and the cleavage rate of comparative example is below 90%, says indirectly
The residual of peroxide is more and odor profiles relatively large in bright comparative example, also corroborates each other and meets with smell test result.
The preparation of the non-fabrication cloth of polypropylene fibre spunbond:
It is non-using 3,7 and 9 raw material polypropylene of above-described embodiment manufacture spunbond on 1 meter wide of 4 production line of Reicofilt
Woven cloths, wherein the production line has single mode head, and every meter of length has about 7000 holes Nuisance, and the diameter in each hole is 0.6mm.If
The yield in fixed each hole is the hole 0.41g//minute.Line speed remains 250m/min.The fabric of the non-woven fabrics of processing
Weight is 12g/m2, the non-woven fabrics is thermally bonded using knurling rolls.
The following table 4 is to manufacture about with embodiment 3, comparative example 4 (embodiment 7) and comparative example 6 (embodiment 9) for Raw material processing
The silk size of non-woven fabrics, processing performance with mechanical performance the data such as related.
Wherein, the avarage fiber diameter in fabric is to measure 20 fibers being selected at random by using optical microscopy
Diameter d is measured.Silk size is to be calculated by following formula relationship from avarage fiber diameter: D=π d2/4×L×ρ×
10-6；The mechanical performance of net is that the tensile strength and elongation of spun-bonded non-woven are measured according to ISO 9073-3:1989 standard
Rate.
From upper table 4 as it can be seen that the non-woven cloth of the acrylic resin institute spunbond of production method provided by the invention preparation reaches
Following effect:
Embodiment 3 can be operated at maximum tank pressure 9900MPa, and silk size is only 1.24 denier under this condition, and
Comparative example 4 (pure hydrogen-regulating method) can only be operated at maximum tank pressure 8100MPa, and silk size is 1.45 denier under this condition,
Also the deviation for observing maximum pressure also in 16% (t≤300h), is much higher than embodiment 3, and the stability of spinning is clearly worse,
Tensility is also more preferable, and spinning speed is improved.
Though comparative example 6 only (directly drops in addition, the silk size of embodiment 3 and 1.26 denier of silk size of comparative example 6 are close
Solution) it can be operated at maximum tank pressure 8500Pa, and the deviation retentivity of 6 maximum pressure of comparative example is far below embodiment
3 (hydrogen tune adds edman degradation Edman), the residue of peroxide is excessively high to keep its stability of spinning process poor, and ultimate tensile strength is also slightly below real
Apply example 3.
In short, should be the result shows that the non-woven cloth of acrylic resin prepared by the present invention institute spunbond (be characterized in that and hydrogen
Tune method compares the polypropylene with the molecular weight distribution more to narrow for spunbond polypropylene, is used for spunbond poly- third with direct edman degradation Edman
Alkene, which is compared, has higher lysis efficiency, less remaining polypropylene of peroxide) have in processability and mechanical properties it is excellent
Gesture.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the above embodiments do not limit the invention in any form, all obtained by the way of equivalent substitution or equivalent transformation
Technical solution is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of production method of high fluidity spun-bonded non-woven acrylic resin, which comprises the following steps:
S1, it catalyst system, hydrogen and propylene is mixed in polymer reactor carries out polymerization reaction, the first product body is made
System, melt index under the conditions of 230 DEG C of temperature, load 2.16kg are 10-15g/10min；
S2, the first product system and additive are mixed, acrylic resin is made by extruder extrusion granulation, in temperature 230
DEG C, the melt index under the conditions of load 2.16kg be 20-45g/10min, molecular weight distributing index Mw/Mn=4-6.
2. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 1, special
Sign is, the polymerization reaction in the step S1, including following operating procedure:
A1, into polymer reactor into propylene, establish partial pressure of propylene to 3.0-3.2MPa,
A2, into polymer reactor into hydrogen to H2/C3Molar ratio be 0.01-0.03 after, to polymer reactor injecting catalyst
System；
After A3, reaction start, it is 3.0-3.2MPa that addition propylene, which keeps polymer reactor inner propene partial pressure, by controlling each material
Inlet amount maintains component ratio；Under the premise of guaranteeing partial pressure of propylene, polymer reactor load is improved to 52t/h；
A4, adjustment H2/C3, first product system of the output melt index in 10-15g/10min.
3. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 1, special
Sign is, the catalyst system include carrier, external electron donor, co-catalyst, internal electron donor, containing titanium-halogen key titanium
Compound；
The external electron donor is alkoxy silane compound, second, isobutyl dimethoxy silane, diisopropyl dimethoxy
Silane, isobutyl methyl dimethoxysilane, tetraethoxysilane, n-propyl triethoxysilane, cyclohexylmethyl dimethoxy
One of base silane；
The internal electron donor be O-phthalic base acid esters, phthalic acid di-n-butyl ester, o-benzene butyl phthalate ester,
9,9- dimethoxy methyl fluorenes, 2,2- diethyl malonic acid di-n-butyl, 2- isobutyl group diethyl maleate, 3,3- dimethyl-penten two
One of diethyl phthalate, di-n-butyl phthalate ester；
The co-catalyst includes triethyl aluminum；
The carrier includes magnesium chloride, magnesium ethylate.
4. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 3, special
Sign is that molar ratio element al and the Si meter of the co-catalyst and external electron donor, the two ratio is 6-10.
5. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 3, special
Sign is that molar ratio element al and the Ti meter of the co-catalyst and catalyst, the two ratio should be 40-600.
6. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 1, special
Sign is, the constituent content of the first product system and additive in the step S2, come by parts by weight in terms of:
First 100 parts of product system, 0.05-0.3 parts of antioxidant, 0.01-0.04 parts of degradation agent, 0.02-0.1 parts of acid absorbent；
The degradation agent includes (2,5- dimethyl -2,5- bis(t-butylperoxy)) hexane；
The acid absorbent includes calcium stearate；
The antioxidant includes primary antioxidant and aid anti-oxidants；
The primary antioxidant is phenolic antioxidant, including 1,3,5- trimethyls -2,4, and (3, the 5- di-t-butyl -4- hydroxyl benzyls of 6- tri-
Base) benzene, at least one of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester,
The aid anti-oxidants are phosphite ester antioxidant, including phosphite ester antioxidant is three (2,4- di-tert-butyl-phenyls)
Phosphite ester.
7. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 1, special
Sign is, 210-240 DEG C of the barrel temperature of extruder in the S2,40-60 DEG C of pelletizing coolant-temperature gage.
8. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 1, special
Sign is that the polymer reactor is Unipol gas-phase polymerization reactor；Reaction temperature is 65-75 DEG C, pressure 2.8-
3.3Mpa。
9. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 1, special
Sign is, cleavage rate CE >=90% of the acrylic resin, CE are limited by following formula I:
。
10. a kind of production method of high fluidity spun-bonded non-woven acrylic resin according to claim 1, special
Sign is that the acrylic resin is applied to the improvement during the production and processing of spun-bonded non-woven, by maximum cabinet air pressure
Power and the holding maximum pressure deviation A in t >=168 hourm≤ 5% come indicate spinning processing stability, wherein improve by with
Lower formula II and formula III is limited:
Am/Bm≥1.1 (II)
ΔAm≤ 5% works as t >=168h (III)
In formula, AmFor the maximum applicable cabinet air pressure [MPa] of acrylic resin of preparation,
BmFor the maximum applicable cabinet air pressure [MPa] of acrylic resin of other methods preparation.
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| 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 |
| CN112521539A (en) * | 2020-11-02 | 2021-03-19 | 中煤陕西榆林能源化工有限公司 | Method for improving granule yield by adjusting powder particle size distribution and granule production system |
| CN112961439A (en) * | 2021-02-10 | 2021-06-15 | 中国神华煤制油化工有限公司 | Polypropylene resin composition, preparation method and application thereof |
| CN113388203A (en) * | 2021-06-30 | 2021-09-14 | 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 |
| CN113968923A (en) * | 2021-11-23 | 2022-01-25 | 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 |
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| 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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| CN113388203A (en) * | 2021-06-30 | 2021-09-14 | 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 |
| 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 |
| CN113968923A (en) * | 2021-11-23 | 2022-01-25 | 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 |
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