CN112812429A - Melt-blown polypropylene material composition and preparation method thereof - Google Patents

Melt-blown polypropylene material composition and preparation method thereof Download PDF

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Publication number
CN112812429A
CN112812429A CN202011634865.5A CN202011634865A CN112812429A CN 112812429 A CN112812429 A CN 112812429A CN 202011634865 A CN202011634865 A CN 202011634865A CN 112812429 A CN112812429 A CN 112812429A
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melt
parts
blown polypropylene
blown
polypropylene material
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许江威
何芳
郑永根
顾华滔
黄锦添
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Guangdong Guoen Plastic Industry Development Co ltd
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Guangdong Guoen Plastic Industry Development Co ltd
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • 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
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    • D—TEXTILES; PAPER
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    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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    • D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract

The invention discloses a melt-blown polypropylene material composition and a preparation method thereof. The melt-blown polypropylene material composition comprises 95-99 parts of melt-blown polypropylene material and 1-5 parts of electret master batch; the polypropylene spraying material comprises the following components: 98-99.85 parts of polypropylene, 0.1-1 part of free radical initiator, 0.05-0.3 part of nucleating agent, 0-0.1 part of antioxidant and 0-0.3 part of lubricant; the electret mother particle comprises the following components: 40-69.5 parts of melt-blown polypropylene, 2-5 parts of waterproof and oil-proof agent, 5-10 parts of softener, 10-15 parts of inorganic electret powder, 10-20 parts of organic electret powder, 1-3 parts of stearate, 1-3 parts of hindered amine weather-resistant agent, 0.5-1 part of antioxidant and 1-3 parts of coupling agent. Because the waterproof oil-proof agent, the softener, the hindered amine weather resistant agent and the antioxidant react with the free radical initiator in the melt-spraying material system, the melt-blown polypropylene and the electret master batch are separately produced and mixed for use; according to the preparation method, the UV lamp box is placed before the material is cut into granules, the material strips are irradiated by the UV lamp, and the peroxide residues which are not completely reacted are completely treated to realize zero peroxide residues.

Description

Melt-blown polypropylene material composition and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to the technical field of engineering plastic modification, and specifically relates to a melt-blown polypropylene material composition and a preparation method thereof.
Background
The ultra-high fluidity polypropylene generally refers to a polypropylene material with extremely high melt index (MI is more than or equal to 500g/10min), and the material is commonly used as a main material of non-woven fabrics in a melt-blown process. Currently, there are generally three processes for preparing ultra-high flow polypropylene. The invention adds peroxide free radical initiator into the conventional polypropylene, and obtains the polypropylene with ultrahigh fluidity (namely, oxygen regulation method) by initiating the degradation reaction of controllable free radical molecular chain fracture. The raw material used by the melt-blown fabric is ultrahigh-flow polypropylene modified by a controllable rheological technology, the typical technical requirement is that the melt index is 1500g/10min, and the filtering efficiency is high. The high fluidity is met, meanwhile, the toughness of the material is reduced obviously, the produced melt-blown fabric is hard in hand feeling and large in brittleness, on one hand, the problem of fracture is easy to occur in the production process, the production efficiency is influenced, and in addition, the wearing experience of the mask produced by using the hard melt-blown fabric is greatly reduced; the oxygen regulation method has peroxide residue which is harmful to human body, and the peroxide residue is generally limited to be less than 5 mg/Kg; in addition, the traditional formula system is difficult to meet the oily filtration index requirements of European and American masks. The present invention has been made in an effort to solve the above-mentioned problems and has been solved, and has a great market application prospect.
Disclosure of Invention
Aiming at the defects of the prior art of the melt-blown polypropylene material, the invention aims at providing the melt-blown polypropylene material composition, the melt-blown cloth produced by the melt-blown polypropylene composition has the advantages of high softness and high filtering efficiency (including oily filtering effect), zero peroxide residue is realized, and the use requirement in the field of masks can be met.
In order to achieve the above purpose, the technical scheme of the invention is as follows: the melt-blown polypropylene material composition comprises the following components in parts by weight:
spraying 95-99 parts of a polypropylene material;
1-5 parts of electret master batch;
the polypropylene spraying material comprises the following components in parts by weight:
Figure RE-GDA0002967096720000021
the electret master batch comprises the following components in parts by weight:
Figure RE-GDA0002967096720000022
the softener is a mixture of special hydrocarbon fluid of non-lead phthalate and low molecular weight polyethylene copolymerized elastomer, the special hydrocarbon fluid is a novel pure paraffin liquid modifier, and the softener can improve the flexibility of the material, reduce the brittleness temperature, improve the elongation at break and improve the transparency; the low molecular weight polyethylene copolymerized elastomer has high fluidity, and the toughness of the material is greatly improved under the condition of not influencing spinning;
the waterproof and oil-proof agent is fluoroalkyl acrylate polymer, and the structural formula is as follows:
Figure RE-GDA0002967096720000031
in the formula:
X——H、-CH3
Y——H、Cl
Figure RE-GDA0002967096720000032
R1——CnH2a-1
Figure RE-GDA0002967096720000033
wherein (A) is a main component of a fluorine-containing water-and oil-repellent agent to impart oil repellency; (B) to impart water resistance and flexibility; (C) is to impart bondability to fibers, abrasion resistance, launderability; (D) the self-crosslinking and the crosslinking with the fiber form a tough surface layer to impart durability. The preparation method comprises the steps of mixing materials in a formula system, performing melt extrusion through a double-screw extruder, placing strips in a UV lamp box before pelletizing, completely treating unreacted peroxide residues, realizing zero peroxide residues, and endowing meltblown fabric with absolute safety performance. The UV lamp box has the power of more than 1000W, the number of the lamp tubes of more than 1 and the main wavelength: 365nm, illumination intensity: 80-200mw/cm2, power supply: 220V, full machine size: 400L (length) 450W (width) 500H (height) mm, a flip-type feed inlet is adopted, and the width is 40CM and the height is 10 CM.
Further, in the above technical scheme, the polypropylene is homo-polypropylene, and the melt index is 10-300g/10min under the test condition of 230 ℃/2.16kg, preferably 25-100g/10 min.
In the above technical solution, the radical initiator is an organic peroxide initiator, and has a general structural formula of R-O-H or R-O-R, wherein R is an alkyl group, an acyl group or a carbonate-based organic group, such as 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, di-t-butyl peroxide, t-butyl peroxybenzoate, and the like.
Further, in the above technical scheme, the active ingredient of the inorganic electret powder is one or more of nano-scale metal oxides or phosphoric acid compounds such as nano tourmaline, fumed silica, fumed alumina, nano zinc oxide, nano titanium dioxide, nano zirconium phosphate, silver-loaded zirconium phosphate and the like.
Further, in the above technical scheme, the active ingredient of the organic electret powder is one or more of an organic fluorine compound, stearate and hindered amine.
Further, in the above technical solution, the nucleating agent is selected from at least one of di-sorbitol and its derivatives, aryl phosphate salts, organic carboxylates, substituted benzamides, and rare earth metal stearates; the polypropylene resin is mainly used for improving the transparency and the surface gloss of polypropylene, particularly diphenyl methylene sorbitol, endows the polypropylene resin with good nucleation efficiency and excellent anti-reflection modification effect, thoroughly eliminates the peculiar smell of the product and improves the thermal stability.
Further, in the above technical scheme, the antioxidant is one or a mixture of two of an antioxidant 1098, an antioxidant 168 and an antioxidant 1010.
Further, in the above technical solution, the lubricant is a mixture of at least one of zinc stearate or calcium stearate and any one or more of ethylene bis stearamide EBS, stearamide, oleamide, calcium stearate, zinc stearate, high boiling paraffin, microcrystalline paraffin, and fatty acid.
A method of preparing a melt blown polypropylene composition comprising the steps of:
(1) according to the proportion, respectively placing the melt-blown polypropylene material formula combination and the electret master batch formula combination into a mixer to be uniformly mixed, wherein the rotating speed of the mixer is 50-150rpm, and the mixing time is 3-10 min;
(2) melting and mixing the mixed raw materials through a double-screw extruder, and extruding and granulating to obtain the melt-blown polypropylene composition, wherein the screw rotating speed of the double-screw extruder is 300-;
(3) the melt-blown polypropylene material is produced by melting and mixing through a double-screw extruder, is extruded into strips, and enters a UV lamp box to irradiate ultraviolet rays after being cooled by cooling water.
The application of the melt-blown polypropylene material is to mix the produced melt-blown polypropylene material and electret master batches according to a proportion and prepare melt-blown non-woven fabrics.
After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects: because the waterproof oil-proof agent, the softener, the hindered amine weather resistant agent and the antioxidant react with the free radical initiator in the melt-spraying material system, the melt-blown polypropylene and the electret master batch are separately produced and mixed for use. The invention also makes certain innovation on the processing equipment for producing the melt-blown material, the preparation method places the UV lamp box before the grain cutting, the material strip is irradiated by the UV lamp, and the peroxide residue which is not completely reacted is completely treated and cleaned, thereby realizing zero peroxide residue. The defects of hard hand feeling and large brittleness of the produced melt-blown fabric are greatly improved by adding the softener into the electret master batch; the fluorine-containing waterproof and oil-proof agent is introduced, so that the produced melt-blown cloth is not easy to absorb moisture and has lasting electricity locking and can resist oil. The melt-blown polypropylene composition prepared by the invention can be used for producing high-performance melt-blown cloth, has high softness and high filtering efficiency (especially high oily filtering effect), and meets the use standard in the field of European and American masks; zero peroxide residue is realized, and the safety of the mask is effectively improved.
Detailed Description
In order to clearly understand the technical means of the present invention and to implement the technical means according to the content of the specification, the following embodiments are further described in detail in the following with reference to the specific examples, which are used for illustrating the present invention and are not intended to limit the scope of the present invention.
Examples and comparative examples:
preparing a melt-blown material:
(1) placing polypropylene, a free radical initiator, a nucleating agent, an antioxidant and a lubricant into a mixer, and uniformly mixing, wherein the rotating speed of the mixer is 100rpm, and the mixing time is 5 min;
(2) and melting and mixing the mixed raw materials through a double-screw extruder, and extruding and granulating to obtain the melt-blown polypropylene, wherein the screw rotating speed of the double-screw extruder is 400rpm, and the melting temperature of the extruder is set to be 180-260 ℃.
Preparing electret master batch:
(1) melt-blown polypropylene, a waterproof and oil-proof agent, a softener, inorganic electret powder, organic electret powder, stearate, a hindered amine weather-resistant agent and an antioxidant are put into a mixer to be uniformly mixed according to the mixture ratio of table 1, the rotating speed of the mixer is 200rpm, and the mixing time is 10 min;
(2) and melting and mixing the mixed raw materials through a double-screw extruder, and extruding and granulating to obtain the electret master batch, wherein the screw rotating speed of the double-screw extruder is 400rpm, and the melting temperature of the extruder is set to be 160-200 ℃.
The compositions prepared in the above specific examples and comparative examples were subjected to melt flow rate (standard GB/T3682-2000, test conditions 230 ℃, 2.16kg) measurement, and melt blown fabrics were prepared by melt blowing equipment; the meltblown fabric grammage (standard FZ-T60003), particle and bacteria filtration efficiency (standard YY0469-2011), softness (standard GB/T8942-2016), breaking strength and elongation at break (FZ-T60005) were further tested, and the performance results are shown in table 2.
TABLE 1 examples and comparative example formulations (parts by weight)
Figure RE-GDA0002967096720000061
TABLE 2 examples and comparative example formulations (parts by weight)
Figure RE-GDA0002967096720000071
As can be seen from Table 2, in example 1, example 2 and example 3, the toughness of the meltblown fabric prepared from the polypropylene composition prepared by the invention through a meltblown device is obviously increased along with the addition of the softener.
As can be seen from table 2, example 1, example 2, example 3 and example 4, the addition of the water-repellent oil-releasing agent greatly increases the oily particle filtration effect, while not affecting the ordinary particle filtration effect.

Claims (10)

1. The melt-blown polypropylene material composition is characterized by comprising the following components in parts by weight:
spraying 95-99 parts of a polypropylene material;
1-5 parts of electret master batch;
the polypropylene spraying material comprises the following components in parts by weight:
Figure RE-FDA0002967096710000011
the electret master batch comprises the following components in parts by weight:
Figure RE-FDA0002967096710000012
the softener is a mixture of special hydrocarbon fluid of non-lead phthalate and low molecular weight polyethylene copolymerized elastomer, and the special hydrocarbon fluid is a novel liquid modifier of pure paraffin;
the waterproof and oil-proof agent is fluoroalkyl acrylate polymer, and the structural formula is as follows:
Figure RE-FDA0002967096710000021
in the formula:
X-H、-CH3
Y-H、Cl
Figure RE-FDA0002967096710000022
m＝3，4，5，6……
R1-CnH2n-1
Figure RE-FDA0002967096710000023
2. a melt-blown polypropylene material composition according to claim 1, wherein the polypropylene is homo-polypropylene and has a melt index of 10-300g/10min, preferably 25-100g/10min at 230 ℃/2.16kg test condition.
3. A melt-blown polypropylene material composition according to claim 1, wherein the free radical initiator is an organic peroxide initiator having a general structural formula of R-O-O-H or R-O-O-R, wherein R is an alkyl group, an acyl group or a carbonate-based organic group and is any one of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, di-t-butyl peroxide and t-butyl peroxybenzoate.
4. The melt-blown polypropylene material composition as claimed in claim 1, wherein the active ingredient of the inorganic electret powder is one or more of nano tourmaline, fumed silica, fumed alumina, nano zinc oxide, nano titanium dioxide, nano zirconium phosphate and silver-loaded zirconium phosphate.
5. The melt-blown polypropylene material composition according to claim 1, wherein the active ingredient of the organic electret powder is one or more of organic fluorine compounds, stearates and hindered amines.
6. The composition of claim 1, wherein the nucleating agent is at least one selected from the group consisting of di-sorbitol and its derivatives, aryl phosphates, organic carboxylates, substituted benzamides, and rare earth stearates.
7. The melt-blown polypropylene composition as claimed in claim 1, wherein the antioxidant is one or a mixture of two of 1098, 168 and 1010.
8. The melt-blown polypropylene composition according to claim 1, wherein the lubricant is at least one of zinc stearate or calcium stearate and a mixture of any one or more of ethylene bis stearamide EBS, stearamide, oleamide, calcium stearate, zinc stearate, high boiling paraffin wax, microcrystalline paraffin wax and fatty acid.
9. A process for the preparation of a composition comprising a melt blown polypropylene material according to any one of claims 1 to 8, comprising the steps of:
(1) respectively placing the melt-blown polypropylene material and the electret master batch into a mixer according to the proportion, and uniformly mixing, wherein the rotating speed of the mixer is 50-150rpm, and the mixing time is 3-10 min;
(2) melting and mixing the mixed raw materials through a double-screw extruder, and extruding and granulating to obtain the melt-blown polypropylene composition, wherein the screw rotating speed of the double-screw extruder is 300-;
(3) the melt-blown polypropylene material is produced by melting and mixing through a double-screw extruder, is extruded into strips, and enters a UV lamp box to irradiate ultraviolet rays after being cooled by cooling water.
10. Use of a composition comprising a melt-blown polypropylene material according to any one of claims 1 to 8, wherein the melt-blown nonwoven fabric is prepared by mixing the melt-blown polypropylene material produced with the electret masterbatch in a ratio.
CN202011634865.5A 2020-12-31 2020-12-31 Melt-blown polypropylene material composition and preparation method thereof Pending CN112812429A (en)

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CN113337964A (en) * 2021-06-03 2021-09-03 上海盈兹无纺布有限公司 Processing method of water electret melt-blown fabric
CN114106458A (en) * 2021-11-17 2022-03-01 中核同辐（长春）辐射技术有限公司 Irradiation modified PP melt-blown material and composite forming process thereof
CN114163732A (en) * 2021-12-31 2022-03-11 广东金发科技有限公司 Melt-blown polypropylene material and preparation method and application thereof
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CN116731426A (en) * 2023-03-31 2023-09-12 广东金发科技有限公司 Melt-blown polypropylene composite material and preparation method and application thereof

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CN113337964A (en) * 2021-06-03 2021-09-03 上海盈兹无纺布有限公司 Processing method of water electret melt-blown fabric
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