CN104558813B - A kind of synthetic method for the polypropene composition being exclusively used in BOPP capacitor films - Google Patents

A kind of synthetic method for the polypropene composition being exclusively used in BOPP capacitor films Download PDF

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CN104558813B
CN104558813B CN201310473088.4A CN201310473088A CN104558813B CN 104558813 B CN104558813 B CN 104558813B CN 201310473088 A CN201310473088 A CN 201310473088A CN 104558813 B CN104558813 B CN 104558813B
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catalyst
capacitor films
synthetic method
bopp
additive
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CN104558813A (en
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刘勇
王荣和
陈国康
赵兰洁
黄飞
虞光财
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China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
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China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a kind of synthetic methods for the polypropene composition being exclusively used in BOPP capacitor films, Ziegler Natta catalyst is used first, using the magnesium chloride of activation as carrier, under the action of major catalyst and co-catalyst, it is polymerize using liquid phase method and generates polypropylene base-material；Then, polypropylene base-material neutralization additive is uniformly mixed, remelted mixing granulation, obtains ultrapure acrylic resin product, can be used for manufacturing BOPP capacitor films.The polypropene composition that the present invention obtains can not only meet the processing technology requirement of manufacture BOPP capacitor films, and can guarantee that the BOPP capacitor films of manufacture have more excellent mechanical performance, high uniformity, high cleaning and electric property.

Description

A kind of synthetic method for the polypropene composition being exclusively used in BOPP capacitor films
Technical field
The present invention relates to a kind of synthetic methods for the polypropene composition being exclusively used in BOPP capacitor films, belong to synthetic resin Technical field.
Background technology
With China's polypropylene（PP）The continuous development of industry, polypropylene application range are further expanded, the low ash of high-purity Component polypropylene resin shows good application prospect in industries such as medicine, electronic apparatus, weavings.Especially electrician uses BOPP Film, lithium battery polypropylene diaphragm are proposed ash content, the metal ion content etc. of pp material harsh requirement.
Biaxially oriented polypropylene (BOPP) film has many characteristics, such as that light, transparent, nontoxic, moisture-proof and mechanical strength is high, extensively The general packaging applied to products such as food, medicine, daily light industry, cigarettes, in addition capacitor dielectric material is also the weight of BOPP film Want one of purposes.Since reform and opening-up, capacitor manufacturing industry is turned to inland of China by Japan, South Korea and Taiwan, World's electronic information complete machine manufacturing industry is set up factories in inland of China, and trans-corporation purchases in inland of China, the production of domestic market complete machine Required capacitor increases by a fairly big margin, and China increasingly becomes the staple market of global capacitor consumption.In addition, capacitor is answered Also constantly expanded with field, Power capacitor industry is interior over the next several years, and there are larger development spaces.
In the evolution of PP production technologies, catalyst plays core impetus.Domestic at present catalyst and Process conditions do not still meet direct polymerization and the low polyacrylic particular/special requirement of ash content are made, often will by using high energy consumption and Expensive washing step.Currently, PP catalyst just can control towards super-active, high directionality and effectively the opposite of polymer Molecular vibrational temperature direction is developed, thus, the few effective catalyst of the high dosage of exploitation activity, and rational process conditions are explored, Reduced as far as possible under conditions of without using washing aftertreatment technology the ash content in polypropylene product be following development trend it One.
Invention content
For overcome the deficiencies in the prior art, the poly- of BOPP capacitor films is exclusively used in the purpose of the present invention is to provide a kind of The synthetic method of propylene compositions, obtained polypropylene resin composite ash content are low.
In the present invention, Ziegler-Natta catalyst is used first, using the magnesium chloride of activation as carrier, in major catalyst Under the action of co-catalyst, it is polymerize using liquid phase method, under conditions of adding less or being not added with external electron donor, propylene is in two sections of rings Polymerisation is carried out in pipe reactor generates acrylic resin base-material.Then, polypropylene base-material neutralization additive is uniformly mixed, Remelted mixing granulation obtains ultrapure acrylic resin product, can be used for manufacturing BOPP capacitor films.Specific technical solution It is described as follows.
What the present invention obtained is exclusively used in the polypropene composition of BOPP capacitor films, is according to Italian BASELL companies SPHERIPOL bis- generations technologies, are prepared using bicyclic pipe tandem reactor.Preparation method includes mainly following step Suddenly：
（1）Pp material enters the first annular-pipe reactor, under the effect of external electron donor, major catalyst and co-catalyst Polymerisation occurs, wherein the pp material is made of propylene and hydrogen, the major catalyst is carried out by HA-DQ and grease It is formulated, quality-volumetric concentration of wherein HA-DQ is 40~100g/l；The co-catalyst is triethyl aluminum, triethyl aluminum It is 0.03~0.15Kg/t with the mass ratio of propylene, the mass ratio of HA-DQ and propylene is 8~20g/t；The external electron donor is Cyclohexyl Methyl Dimethoxysilane, mass ratio≤3 of 0≤cyclohexyl methyl dimethoxy and triethyl aluminum：1；
（2）First annular-pipe reactor outlet material is entered into the second annular-pipe reactor and carries out polymerisation, obtains polypropylene-base Material；
（3）To step（2）Additive is added in obtained polypropylene base-material, after evenly mixing, is melted with extruder Mixing granulation, then homogenizing obtain produce for BOPP capacitor films it is resin dedicated, melting heating temperature be 200~260 DEG C.
Above-mentioned steps（1）In the HA-DQ of middle use, the mass content of titanium is 2.5~3.0%, and the quality of internal electron donor contains Amount is 10~25%, and the mass content of magnesium chloride is 72~87.5%.The grease is vaseline.
Above-mentioned steps（1）And step（2）When middle progress polymerisation, reaction temperature is 65~75 DEG C, reaction pressure 3.3 ~4.4MPa, endless tube density are 520~570Kg/m3, and powder melt flow rate (MFR) is 3.2~4.4g/min, and density of hydrogen is 300~900ppm.
Above-mentioned steps（1）In, endless tube density is preferably 540~570Kg/m3；The mass ratio of triethyl aluminum and propylene is preferred For 0.03~0.08Kg/t.
Above-mentioned steps（3）In, the additive includes primary antioxidant and auxiliary anti-oxidant, acid neutralizing agent, wherein：
The primary antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；
The auxiliary anti-oxidant is without phosphorus azanol kind antioxidant [N.N diethyl phenyls] azanol；
The efficient acid neutralizing agent is synthetic hydrotalcite DHT-4A；The component proportion of the additive in parts by weight, When primary antioxidant is 100 parts, 50~100 parts of auxiliary anti-oxidant, efficient acid neutralizing agent is 15 parts.
The weight ratio of above-mentioned acrylic resin base-material and additive is（500~2000）：1.
Inventor has found through numerous studies, using high activated catalyst HA-DQ catalyst, reduces co-catalysis in traditional handicraft The addition of agent triethyl aluminum improves annular-pipe reactor density under conditions of adding less or being not added with external electron donor, can be substantially Degree reduces the ash of resin.
The advantage of the invention is that：The melt index for the polypropylene resin composite that the present invention synthesizes 2.0~ Between 4.0g/10min；With high isotactic, isotacticity is 95.0~98.0%；Ash content is low, and ash is less than 40ppm, can be special In the production of BOPP capacitor films；When being exclusively used in the production of BOPP capacitor films, the mechanicalness of PP Pipe Compound can be effectively improved Energy, high uniformity, high cleaning and electric property.
Below will by specific embodiment, the invention will be further described, the definition of ash is such as wherein in invention Under：
Ash：Combustion of organic matter and at high temperature calcination processing residue are until constant weight.Ash based on mass fraction, numerical value It is indicated with %, calculation formula is as follows：
Ash content（%）=m1、m0*100
In formula：m0--- dry sample mass, unit are gram（g）；m1--- gained ash weight, unit are gram（g）.Attached drawing Explanation
Fig. 1 is the present invention for synthesizing the resin dedicated schematic device of BOPP capacitor films.
Figure label：D201 pre-contact tank, R200 pre-polymerization reactors, the first annular-pipe reactors of R201, the second rings of R202 Pipe reactor, D301 high pressures degassing tank, F301 bag filters, D501 steamers, D502 driers, EX801 extruders.
Specific implementation mode
In the present invention, HA-DQ commercially, is produced by Beijing Chemical Research Institute, and the mass content of titanium is in HA-DQ 2.5~3.0%, the mass content of internal electron donor is 10~25%, and the mass content of magnesium chloride is 72~87.5%；
Major catalyst is formulated by HA-DQ and vaseline, and quality-volumetric concentration of HA-DQ is 40~100g/l
The present invention is resin dedicated using Fig. 1 shown devices synthesis BOPP capacitor films.
【Examples 1 to 8】
A kind of method that synthesis BOPP capacitor films are resin dedicated is provided in the present invention, is mainly included the following steps that：
1）Pp material（Predominantly propylene contains appropriate amount of hydrogen）Into the first annular-pipe reactor, in external electron donor, master Catalyst is 65~75 DEG C with the lower generation polymerisation of co-catalyst effect, reaction temperature, and reaction pressure is .3~4.4MPa, ring Pipe density is 520~570Kg/m3, and powder melt flow rate (MFR) is 3.2-4.4g/min, and density of hydrogen is 300~900ppm；
2）First annular-pipe reactor outlet material enters the second annular-pipe reactor and carries out polymerisation, obtains polypropylene base-material, Reaction temperature is 65~75 DEG C, and reaction pressure is 3.3~4.4MPa, and endless tube density is 520~570Kg/m3, powder melt flows Rate is 3.2~4.4g/min, and density of hydrogen is 300~900ppm；
3）In step 2）Additive is added in obtained polypropylene base-material, and additive includes primary oxidant（Four [β-(3,5- Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester）, cooxidant（[N.N diethyl phenyls] azanol）With efficiently remove Sour agent（DHT-4A）, when primary antioxidant is 100 parts, 50~100 parts of auxiliary anti-oxidant, efficient acid absorbent is 15 parts,
The mass ratio of the polypropylene base-material and additive is（500~2000）：1, extruded machine progress after evenly mixing Melting mixing is granulated, and then it is resin dedicated to obtain low ash polypropylene fibre for homogenizing, and melting heating temperature is 200~260 DEG C.
Each embodiment material proportion is shown in Table 1, and reaction process condition is shown in Table 2, table 3, table 4, obtained acrylic resin product The performance test results be shown in Table 5.Melt index is tested：Instrument melting means index tester is tested using GB/T3682 methods.
【Comparative example 1~2】
Acrylic resin is synthesized using traditional synthesis technology, electron donor is being added and is not controlling co-catalyst dosage Acrylic resin is synthesized under process conditions.Comparative example 1 and comparative example 2 are using commercially available DQ series catalysts.
Table 1
Table 2
Table 3
Table 4
Table 5

Claims (5)

1. a kind of synthetic method for the polypropene composition being exclusively used in BOPP capacitor films, which is characterized in that include mainly following Step：
(1) pp material enters the first annular-pipe reactor, occurs under the effect of external electron donor, major catalyst and co-catalyst Polymerisation, wherein the pp material is made of propylene and hydrogen, the major catalyst is prepared by HA-DQ and grease It forms, quality-volumetric concentration of wherein HA-DQ is 40~100g/l；The co-catalyst is triethyl aluminum, triethyl aluminum and third The mass ratio of alkene is 0.03~0.15Kg/t, and the mass ratio of HA-DQ and propylene is 8~20g/t；The external electron donor is hexamethylene Ylmethyl dimethoxysilane, mass ratio≤3 of 0≤cyclohexyl methyl dimethoxy and triethyl aluminum：1；
(2) the first annular-pipe reactor outlet material is entered into the second annular-pipe reactor and carries out polymerisation, obtain polypropylene base-material；
(3) additive is added in the polypropylene base-material obtained to step (2), after evenly mixing, melting mixing is carried out with extruder It is granulated, then homogenizing obtains producing for BOPP capacitor films resin dedicated, and melting heating temperature is 200~260 DEG C；
When carrying out polymerisation in step (1) and step (2), reaction temperature is 65~75 DEG C, reaction pressure is 3.3~ 4.4MPa, endless tube density are 520~570Kg/m3, and powder melt flow rate (MFR) is 3.2~4.4g/min, density of hydrogen 300 ~900ppm；
In HA-DQ described in step (1), the mass content of titanium is 2.5~3.0%, the mass content of internal electron donor is 10~ 25%, the mass content of magnesium chloride is 72~87.5%；The grease is vaseline.
2. synthetic method according to claim 1, it is characterised in that：In step (1) and step (2), the endless tube density For 540~570Kg/m3.
3. synthetic method according to claim 1, it is characterised in that：The matter of triethyl aluminum and propylene described in step (1) Amount is than being 0.03~0.08Kg/t.
4. synthetic method according to claim 1, it is characterised in that：Step 3) the additive includes primary antioxidant, auxiliary Antioxidant and efficient acid neutralizing agent, wherein：
The primary antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；
The auxiliary anti-oxidant is without phosphorus azanol kind antioxidant [N.N diethyl phenyls] azanol；
The efficient acid neutralizing agent is synthetic hydrotalcite DHT-4A；
In parts by weight, when primary antioxidant is 100 parts, auxiliary anti-oxidant is 50~100 parts to the component proportion of the additive, Efficient acid neutralizing agent is 15 parts.
5. synthetic method according to claim 1, it is characterised in that：The weight ratio of the polypropylene base-material and additive is (500~2000)：1.
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CN109306030A (en) * 2017-07-28 2019-02-05 中国石油天然气股份有限公司 Special material for lithium battery diaphragm and preparation method thereof
CN109575171B (en) * 2018-10-09 2022-09-09 中国石油化工股份有限公司 Preparation method of polypropylene cast film resin
CN111100371A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Homo-polypropylene material for power cable and preparation method thereof
CN111100382A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Polypropylene-butadiene copolymer material for power cable and preparation method thereof
CN112876591A (en) * 2021-02-26 2021-06-01 陕西延长中煤榆林能源化工有限公司 Industrial production method of polypropylene resin for battery diaphragm
KR20240149394A (en) 2022-01-06 2024-10-14 차이나 페트로리움 앤드 케미컬 코포레이션 Biaxially oriented polypropylene dielectric film, modified polypropylene material and uses thereof
CN115160463B (en) * 2022-06-24 2023-07-28 中国石化中原石油化工有限责任公司 Method for producing polypropylene with high purity and low precipitate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0415229A (en) * 1990-05-08 1992-01-20 Mitsubishi Petrochem Co Ltd Biaxially oriented polypropylene film
CN1718598A (en) * 2005-07-22 2006-01-11 白跃华 Preparation method of homopolymerization polypropylene bidirection drawing film special material
CN1810871A (en) * 2005-01-28 2006-08-02 中国石油化工股份有限公司 Polypropylene composition and the biaxial stretching film prepared thereof
CN101389705A (en) * 2006-02-22 2009-03-18 Ls电线有限公司 Propylene resin composition with flame retardance and abrasion resistance

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130295395A1 (en) * 2012-04-27 2013-11-07 Claudio M. Paulino Biaxially oriented polypropylene film with improved moisture barrier

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0415229A (en) * 1990-05-08 1992-01-20 Mitsubishi Petrochem Co Ltd Biaxially oriented polypropylene film
CN1810871A (en) * 2005-01-28 2006-08-02 中国石油化工股份有限公司 Polypropylene composition and the biaxial stretching film prepared thereof
CN1718598A (en) * 2005-07-22 2006-01-11 白跃华 Preparation method of homopolymerization polypropylene bidirection drawing film special material
CN101389705A (en) * 2006-02-22 2009-03-18 Ls电线有限公司 Propylene resin composition with flame retardance and abrasion resistance

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
我的兴趣只在科研上;梁晓云等;《中国石化报》;20111028;第1-2页 *
聚丙烯拉丝树脂的生产与应用;逢锦屹等;《合成树脂及塑料》;20101125;第27卷(第6期);第38-40页 *

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