CN114013140A - Permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability and preparation method and application thereof - Google Patents
Permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability and preparation method and application thereof Download PDFInfo
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- CN114013140A CN114013140A CN202111339874.6A CN202111339874A CN114013140A CN 114013140 A CN114013140 A CN 114013140A CN 202111339874 A CN202111339874 A CN 202111339874A CN 114013140 A CN114013140 A CN 114013140A
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- 229920006379 extruded polypropylene Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 6
- -1 polypropylene Polymers 0.000 claims abstract description 79
- 239000004743 Polypropylene Substances 0.000 claims abstract description 73
- 229920001155 polypropylene Polymers 0.000 claims abstract description 68
- 239000002216 antistatic agent Substances 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000002667 nucleating agent Substances 0.000 claims abstract description 14
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 230000001050 lubricating effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920002614 Polyether block amide Polymers 0.000 claims description 4
- 238000010008 shearing Methods 0.000 claims description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000000454 talc Substances 0.000 abstract 1
- 229910052623 talc Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 80
- 239000000047 product Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 12
- 239000004033 plastic Substances 0.000 description 12
- 238000012545 processing Methods 0.000 description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 244000198896 Lagerstroemia speciosa Species 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/21—Anti-static
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
A dimensionally stable, permanently antistatic three-layer co-extruded polypropylene sheet comprising: a. the materials of the upper antistatic layer and the lower antistatic layer comprise the following components in parts by weight: 65-85 parts of polypropylene resin; 10-30 parts of a permanent antistatic agent; 0-5 parts of a lubricating compatilizer; 0.5-2 parts of a processing aid; b. the intermediate layer material comprises the following components in percentage by weight: 80-100 parts of polypropylene resin; 0-20 parts of superfine talc; 0-1 part of nucleating agent; 0-1 part of processing aid. The advantages are that: the problems of film forming and hole breaking and permanent antistatic are solved; the problem of poor dimensional stability of the polypropylene sheet is solved.
Description
Technical Field
The invention relates to the field of extruded sheets, in particular to a permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability and a preparation method and application thereof.
Background
In the processes of processing, packaging, storing and transporting components in electronic and electric appliances, the components are easily damaged due to static electricity generated in the friction process of a packaging and storing material, and therefore the packaging material related to the components needs to be subjected to anti-static treatment. Polypropylene has good ductility in a molten state, can be used for making three-layer co-extruded sheets, but the pure polypropylene has low crystallization temperature, slow crystallization rate and large shrinkage rate, so that when the sheets are processed into products, the required pressure maintaining time in the plastic suction process is long, and the plastic suction processing efficiency of the three-layer polypropylene sheets is greatly reduced. Meanwhile, the prepared blister product is easy to deform under the influence of after-shrinkage and residual stress, so that the problem of poor dimensional stability of the blister product is caused.
A packaging material for mounting electronic parts and components requires a surface resistance of 108Omega. Because polypropylene is prone to static electricity, polypropylene sheet applications in the electronics packaging industry require the addition of antistatic agents.
The micromolecule migration type non-permanent antistatic agent is difficult to achieve an effective antistatic effect in a dust-free clean workshop environment with low humidity, and the micromolecule antistatic agent on the surface of a product can be continuously consumed due to wiping and washing, so that the electronic packaging material can not be used for a half year generally. The black conductive carbon black or conductive graphite antistatic agent needs to be added in a large amount to form a conductive network, although the surface resistance can reach 106Hereinafter, howeverThe carbon black and graphite which belong to inorganic fillers have poor compatibility with nonpolar polypropylene, the prepared sheet is easy to remove powder, thereby polluting electronic components and clean workshops, and large addition amount can also greatly influence the toughness of the material.
The macromolecular permanent antistatic agent contains a polyethylene glycol ether structure in a polymer molecular structure, achieves an antistatic effect through interaction with chelated alkali metal salt, has low dependence of permanent antistatic property on air humidity, and meets the processing requirement of electronic components in a low-humidity clean workshop. However, the permanent antistatic agent has the problems of large addition amount, high price and the like, and in order to reduce the use cost of materials, a three-layer co-extrusion sheet equipment process is used for preparing the permanent antistatic polypropylene sheet. Meanwhile, because the macromolecule permanent antistatic agent has strong molecular polarity and is difficult to be compatible with non-polar polyolefin, the upper layer and the lower layer which are co-extruded by three layers are difficult to form a film by extrusion processing under the condition of simply adding a compatilizer, the surface effect of the sheet can be seriously influenced, and holes, crystal points and layering are generated, so that the surface resistance stability and the appearance of the sheet are influenced.
Disclosure of Invention
The invention aims to overcome the defects that the PP sheet material in the prior art is poor in size stability and antistatic effect, and the sheet appearance and surface resistance are influenced by poor film-forming property of an antistatic layer due to poor compatibility of a conventional block polyesteramide high-molecular permanent antistatic agent and polypropylene, and provides a permanent antistatic three-layer co-extruded polypropylene sheet material with size stability, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a dimensionally stable, permanently antistatic three-layer co-extruded polypropylene sheet comprising:
a. the materials of the upper antistatic layer and the lower antistatic layer comprise the following components in parts by weight:
65-85 parts of polypropylene resin;
10-30 parts of a permanent antistatic agent;
0-5 parts of a lubricating compatilizer;
0.5-2 parts of a processing aid;
b. the intermediate layer material comprises the following components in percentage by weight:
80-100 parts of polypropylene resin;
0-20 parts of superfine talcum powder;
0-1 part of nucleating agent;
0-1 part of processing aid.
Further, the polypropylene is a mixture of medium-high viscosity homopolymerized polypropylene and ultrahigh-viscosity high-impact copolymerized polypropylene; wherein the medium-high viscosity homo-polypropylene accounts for 40-50 parts; 25-35 parts of ultrahigh-viscosity high-impact copolymerized polypropylene.
Further, the permanent antistatic agent a is a polymer block polyether ester permanent antistatic agent or a block polyether amide permanent antistatic agent.
Further, the lubricating compatilizer is GMA grafted polyethylene wax with an ultrahigh grafting rate of 3-5%.
Further, the polypropylene b is medium-high viscosity high impact co-polypropylene.
Further, b, the particle size of the superfine talcum powder is 1-3 um, and the superfine talcum powder is coated by a surface treating agent.
Further, the nucleating agent b is a mixture of inorganic and organic.
A method for preparing a permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability comprises the following steps:
s1, drying the permanent antistatic agent, fully stirring and uniformly mixing the materials of the rest components a, shearing, dispersing and granulating by a double-screw extruder, and finally drying;
s2, fully and uniformly stirring the materials of the component b, shearing, dispersing, extruding, granulating and drying by using a double-screw extrusion granulator;
s3, correspondingly conveying the dried materials in the S1 and the S2 to an upper layer feeding tank, a lower layer feeding tank and a middle layer feeding tank of a three-layer co-extrusion three-screw extruder respectively, wherein the thickness of the upper layer and the lower layer of the sheet is adjusted according to the extrusion amount of the screws corresponding to the upper layer and the lower layer;
s4, extruding the melted material in the S3 into a pull tab through a three-layer die head of a three-screw extruder for three-layer co-extrusion;
the S5 sheet was drawn, shaped, cooled and wound up by a pulling roll.
An application of a permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability in the aspect of preparing electronic and electric appliances.
The invention has the beneficial effects that: the upper layer and the lower layer of the three-layer co-extruded polypropylene sheet prepared by adding the macromolecular permanent antistatic agent and the compatible lubricant with high grafting rate into polypropylene solve the problems of film forming hole breaking and permanent antistatic and achieve the effects of film forming without hole breaking and permanent antistatic; the middle layer of the three-layer co-extruded polypropylene sheet prepared by adding superfine talcum powder and nucleating agent into polypropylene solves the problem of poor dimensional stability of the polypropylene sheet, and the surface resistance of the sheet is 1.5 multiplied by 108Omega, the effect of high dimensional stability of the polypropylene sheet is achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The raw materials used in the following examples are as follows;
polyolefin resin a 1: polypropylene, PP T03S, majesty;
polyolefin resin a 2: the high-impact ultralow-solubility block copolymer polypropylene and the low-solubility homopolymerization polypropylene are prepared according to the proportion of 1:2, the high-impact ultralow-solubility block copolymer polypropylene, PP 3003, Taiwan plastic rubber, the low-solubility homopolymerization polypropylene, PP T03S, named as petrochemical;
polyolefin resin B: the high impact low solubility refers to block copolymer polypropylene, PP K8003, Yanshan petrochemical;
permanent antistatic agent A: 10g/10min of block polyether amide type permanent antistatic agent, PAT-3002, Nanjing Mingxin New Material science and technology Limited;
permanent antistatic agent B: the block polyether ester type permanent antistatic agent is 10g/10min, PAT-5501, Nanjing Mingxin New Material science and technology Co., Ltd;
lubricating compatibilizer a: polyethylene wax with GMA grafting rate, 5 percent of GMA grafting rate and a new Xeno material.
Lubricating compatilizer B: polyethylene wax with GMA grafting rate of 8 percent and a Xeno new material.
Superfine talcum powder A: the average particle diameter was 3 μm, and the product was treated with a silane coupling agent and commercially available.
Superfine talcum powder B: the average particle diameter was 5 μm, and the product was treated with a silane coupling agent and commercially available.
A nucleating agent A: a mixture of inorganic and organic nucleating agents, P250, brungelmann, germany.
Processing aid: antioxidant, lubricant mixture.
Antioxidant: antioxidant 1010, antioxidant 168, and linaloon.
Lubricant: EBS ethylene bis stearamide, queen flower.
The present invention will be described in detail with reference to examples.
The following embodiment prepares a permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability by the following method, and the components are weighed according to the weight ratio in tables 1-3, and the specific steps are as follows:
s1, drying a permanent antistatic agent:
the temperature of the drying treatment is between 80 ℃, and the drying time is 4 hours:
s2, uniformly mixing the material dried in the step S1, polypropylene, the compatilizer and the processing aid in a stirring tank, and conveying the mixture to a double-screw extruder with the length-diameter ratio of at least 44:1 for melting, plasticizing, extruding and granulating.
And S3, drying the granules granulated in the step S2 in a drying tank, wherein the temperature of the drying tank is 90 ℃, and the drying time is 6 hours.
S4, uniformly mixing the polypropylene, the superfine talcum powder, the nucleating agent and the processing aid in a stirring tank, and conveying the mixture to a double-screw extruder with the length-diameter ratio of at least 44:1 for melting, plasticizing, extruding and granulating.
S5, drying the granules granulated in the step S4 in a drying tank, wherein the temperature of the drying tank is 105 ℃, and the drying time is 2 hours.
6. Respectively melting and plasticizing the materials in the S3 and the S5 by a screw of a three-layer extrusion sheet machine, then feeding the materials into corresponding multi-layer structure die heads, extruding the melt through an oral die, wherein the upper layer and the lower layer are the materials in the S3, the middle layer is the materials in the S5, and the material conveying ratio is adjusted according to the required thickness of the surface layer.
S7, drawing, rolling, stretching and cooling the melt through a drawing roller.
And S8, rolling and packaging the sheet.
Examples 1 to 4
Table 1 formulations (parts) of examples 1 to 4, wherein the upper and lower layers in the examples represent formulations for the upper and lower layers of a three-layer sheet, and the middle layer formulation in the examples represents formulation for the middle layer.
Examples 5 to 8
TABLE 2 formulations (parts) of examples 5 to 8
Examples 9 to 12
TABLE 3 formulations (parts) of examples 9 to 12
Examples 13 to 16
TABLE 4 formulations (parts) of examples 13 to 16
The modified polypropylene particles prepared in the above examples 1 to 16 were subjected to melt index, shrinkage, glass transition temperature, flexural modulus, and notched impact test, and the reference standards and methods for the test were as follows:
determination of melt index: according to the method provided by GB/T3682, the permanent antistatic agent is tested under the temperature condition of 190 ℃ and the weight of the permanent antistatic agent is 2.16 kg.
Measurement of shrinkage ratio: according to the method provided by GB/T15585.
Measurement of glass transition temperature: according to the method provided by GB/T1634.
And (3) flexural modulus measurement: according to the method provided in GB/T9341.
Notched impact determination: according to the method provided in GB/T1043.
Table 4 example data
The three-layer co-extruded polypropylene sheet with the permanent antistatic property and the dimensional stability prepared in the embodiments 1 to 16 is subjected to a surface resistance test, the sheet is subjected to surface film defects and whether precipitates exist or not is evaluated, the sheet is subjected to a cycle test in a plastic suction processing process, and the deformation of a plastic suction product is evaluated.
Sheet surface resistance measurement: according to the method provided by GB/T12703.4-2010, the temperature condition is 25 ℃, and the humidity condition is 50% RH.
And (3) evaluating the surface appearance defects of the sheet: according to the method provided by the quality control standard in an enterprise, whether the surface of the sheet is broken, whether crystal points exist or not and whether the upper layer, the lower layer and the middle layer are layered or not are recorded.
And (3) sheet plastic uptake processing efficiency determination: and recording the pressure maintaining time required by the blister processing according to the method provided by the internal control quality standard of the enterprise.
Measuring the dimensional tolerance of the sheet plastic uptake product: according to the method provided in GB/T14486-2008.
Table 5 example data
In examples 1 to 3, the density of the dispersed phase permanent antistatic agent decreased with the increase of the polypropylene resin content in the upper and lower layers, the formed conductive path decreased, and the surface resistivity increased.
From examples 1 and 4 to 5, the crystallization temperature of the polypropylene in the intermediate layer gradually increases with the increase of the polypropylene content in the intermediate layer, the pressure holding time required by the corresponding sheet during the plastic suction processing slightly increases, and the plastic suction product does not deform.
From examples 1 and 6 to 7, it can be seen that, as the amount of the permanent antistatic agent in the upper and lower layers is increased, the dispersion density of the permanent antistatic agent in the thin film layer is increased, the sheet surface resistivity is reduced, and the film forming effect is stable.
From examples 1 and 8 to 9, the type of the permanent antistatic agent has a serious influence on the surface and surface resistance of the prepared three-layer permanent antistatic sheet, wherein the permanent antistatic agent of the polyether amide with stronger polarity cannot achieve good compatibility and dispersion effects under the action of the GMA grafted polyethylene wax compatible lubricant, so that the strength of the material is insufficient during melting, and holes are broken or a film cannot be formed in the film forming process.
From examples 1 and 10, when the amount of GMA-grafted polyethylene wax used was reduced from 5% to 3%, the appearance of the surface of the sheet produced showed problems of hole breakage, crystal point, and surface resistance was also reduced.
From examples 1 and 11, the polyethylene wax grafted with low content of 3% of GMA is used as a compatible lubricant, and the prepared sheet has the problems of hole breakage, crystal points and delamination, which shows that the polyethylene wax with 3% of GMA grafting rate can greatly reduce the compatibility of polypropylene and the block ether ester polymer permanent antistatic agent.
From examples 1 and 12 to 13, as the content of the ultrafine talc powder in the intermediate layer increases, the shrinkage rate of the intermediate layer material decreases, the crystallization temperature increases greatly, the efficiency of the blister processing process of the sheet is greatly improved, and meanwhile, the dimensional stability of the manufactured sheet is also high, but when the content of the talc powder is 20%, the notch impact of the material is greatly reduced, so that the product becomes brittle.
From examples 1 and 14, as the particle size of the talc powder of the intermediate layer increases, the shrinkage of the material of the intermediate layer increases slightly, the crystallization temperature decreases slightly, and the notch impact of the material decreases
From embodiment 1 and 15 ~ 16, along with the increase of nucleating agent content, can increase substantially the crystallization temperature of material to a certain extent, the plastic uptake machining efficiency of effectual improvement sheet also can improve product dimensional stability greatly simultaneously.
Embodiment 17 a permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability, comprising the following upper and lower permanent antistatic layers in parts by weight:
65-85 parts of polypropylene resin;
10-30 parts of a permanent antistatic agent;
2-5 parts of a lubricating compatilizer;
0.5-2 parts of a processing aid.
The middle layer comprises the following components in parts by weight:
60-80 parts of polypropylene resin;
15-35 parts of superfine talcum powder;
5-10 parts of a toughening agent;
0.5-2 parts of a nucleating agent;
0.5-2 parts of a processing aid.
Generally, polar high-molecular permanent antistatic agent polymers have poor compatibility with nonpolar polypropylene, so that the permanent antistatic agent is difficult to uniformly disperse in the polypropylene in the stretching and film-forming process of a molten material of an upper antistatic layer and a lower antistatic layer, and finally, a plurality of holes, crystal points and layers with nonuniform sizes exist on the upper surface and the lower surface of a three-layer co-extruded sheet.
According to the invention, GMA grafted polyethylene wax with compatibility and lubrication functions is adopted to improve the antistatic property and surface defects of a three-layer co-extruded polypropylene sheet prepared by using a block polyether ester permanent antistatic agent, and on one hand, the permanent antistatic effect is achieved by adding a high-molecular permanent antistatic agent into polypropylene resin; on the other hand, the compatilizer with high grafting ratio content and excellent lubricity is adopted to solve the problems of compatibility and lubricating dispersibility of the permanent antistatic agent in the film forming process of polypropylene, prevent the appearance defect of the surface of the sheet, and ensure the surface resistance stability of the prepared sheet.
A permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability is disclosed, wherein the polypropylene is a mixture of medium-viscosity polypropylene and ultrahigh-viscosity polypropylene.
A permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability is provided, wherein polypropylene with medium viscosity is homo-polypropylene, the melt index is 3-5 g/10min,
the permanent antistatic three-layer co-extruded polypropylene sheet with stable size has high impact and high viscosity of polypropylene copolymer and melting index of 0.03g/10 min.
The permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability comprises 50-60 parts of medium-viscosity polypropylene and 15-25 parts of high-impact ultrahigh-viscosity polypropylene.
The permanent antistatic three-layer co-extruded polypropylene sheet with stable size is characterized in that the permanent antistatic agent is a high-molecular permanent antistatic agent of block polyether ester, and the melt index is 15g/10 min.
A permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability is characterized in that a compatible lubricant is polyethylene wax grafted by GMA (glycidyl methacrylate), the molecular weight is 2000, and the GMA grafting rate is 8%.
According to the invention, the superfine talcum powder is filled to reduce the shrinkage rate of the polypropylene, and is compounded with the nucleating agent for use, so that the crystallization temperature and the crystallization nucleation rate of the polypropylene are synergistically improved, the pressure maintaining time of the polypropylene sheet in the plastic uptake processing process is shortened, the processing efficiency is improved, and the product size stability of the polypropylene sheet after the plastic uptake processing into a product is effectively improved.
The permanent antistatic three-layer co-extruded polypropylene sheet with stable size is characterized in that the average particle size of superfine talcum powder is 1-3 um, and the superfine talcum powder is subjected to surface modification treatment by a coupling agent.
A permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability is disclosed, wherein the coupling agent is one of silane or titanate.
The permanent antistatic three-layer co-extruded polypropylene sheet with stable size has the nucleating agent of one inorganic and organic mixture.
The invention also provides a preparation method of the permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability, which comprises the following steps:
s1, drying a permanent antistatic agent:
the temperature of the drying treatment is 75-85 ℃, and the drying time is 4-6 hours:
s2, uniformly mixing the material dried in the step S1, polypropylene, the compatilizer and the processing aid in a stirring tank, and conveying the mixture to a double-screw extruder with the length-diameter ratio of at least 44:1 for melting, plasticizing, extruding and granulating.
And S3, drying the granules granulated in the step S2 in a drying tank, wherein the temperature of the drying tank is 80-90 ℃, and the drying time is 6-8 hours.
S4, uniformly mixing the polypropylene, the superfine talcum powder, the nucleating agent and the processing aid in a stirring tank, and conveying the mixture to a double-screw extruder with the length-diameter ratio of at least 44:1 for melting, plasticizing, extruding and granulating.
And S5, drying the granules granulated in the step S4 in a drying tank, wherein the temperature of the drying tank is 95-105 ℃, and the drying time is 2-4 hours.
And S6, respectively melting and plasticizing the materials in the S3 and the S5 by a screw of a three-layer sheet extruding machine, then feeding the materials into a corresponding multi-layer structure die head, extruding a melt through an oral die, wherein the upper layer and the lower layer are the materials in the S3, the middle layer is the materials in the S5, and the material conveying proportion is adjusted according to the required thickness of the surface layer.
S7, drawing, rolling, stretching and cooling the melt through a drawing roller.
And S8, rolling and packaging the sheet.
Preferably, sealed packaging is performed.
An application of a permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability in preparing antistatic trays and electric appliance shells.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention and the equivalent alternatives or modifications according to the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (9)
1. The permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability is characterized in that: comprises the following steps:
a. the materials of the upper antistatic layer and the lower antistatic layer comprise the following components in parts by weight:
65-85 parts of polypropylene resin;
10-30 parts of a permanent antistatic agent;
0-5 parts of a lubricating compatilizer;
0.5-2 parts of a processing aid;
b. the intermediate layer material comprises the following components in percentage by weight:
80-100 parts of polypropylene resin;
0-20 parts of superfine talcum powder;
0-1 part of nucleating agent;
0-1 part of processing aid.
2. The dimensionally stable, permanently antistatic tri-layer coextruded polypropylene sheet of claim 1 wherein: a, the polypropylene is a mixture of medium-high viscosity homopolymerized polypropylene and ultrahigh viscosity high impact copolymerization polypropylene; wherein the medium-high viscosity homo-polypropylene accounts for 40-50 parts; 25-35 parts of ultrahigh-viscosity high-impact copolymerized polypropylene.
3. The dimensionally stable, permanently antistatic tri-layer coextruded polypropylene sheet of claim 1 wherein:
the permanent antistatic agent is a polymer block polyether ester permanent antistatic agent or a block polyether amide permanent antistatic agent.
4. The dimensionally stable, permanently antistatic tri-layer coextruded polypropylene sheet of claim 1 wherein: a, the lubricating compatilizer is GMA grafted polyethylene wax with an ultra-high grafting rate of 3-5%.
5. The dimensionally stable, permanently antistatic tri-layer coextruded polypropylene sheet of claim 1 wherein: b, the polypropylene is medium-high viscosity high impact copolymerized polypropylene.
6. The dimensionally stable, permanently antistatic tri-layer coextruded polypropylene sheet of claim 1 wherein: b, the particle size of the superfine talcum powder is 1-3 um, and the superfine talcum powder is coated by a surface treating agent.
7. The dimensionally stable, permanently antistatic tri-layer coextruded polypropylene sheet of claim 1 wherein: b the nucleating agent is a mixture of inorganic and organic.
8. A method for preparing the dimensionally stable, permanently antistatic three-layer co-extruded polypropylene sheet as claimed in any one of claims 1 to 7, which comprises the following steps:
s1, drying the permanent antistatic agent, fully stirring and uniformly mixing the materials of the rest components a, shearing, dispersing and granulating by a double-screw extruder, and finally drying;
s2, fully and uniformly stirring the materials of the component b, shearing, dispersing, extruding, granulating and drying by using a double-screw extrusion granulator;
s3, correspondingly conveying the dried materials in the S1 and the S2 to an upper layer feeding tank, a lower layer feeding tank and a middle layer feeding tank of a three-layer co-extrusion three-screw extruder respectively, wherein the thickness of the upper layer and the lower layer of the sheet is adjusted according to the extrusion amount of the screws corresponding to the upper layer and the lower layer;
s4, extruding the melted material in the S3 into a pull tab through a three-layer die head of a three-screw extruder for three-layer co-extrusion;
the S5 sheet was drawn, shaped, cooled and wound up by a pulling roll.
9. Application of the permanent antistatic three-layer co-extruded polypropylene sheet with dimensional stability as defined in any one of claims 1 to 7 in preparation of electronic and electric appliances.
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Cited By (1)
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| CN115160693A (en) * | 2022-07-21 | 2022-10-11 | 建德市华丰环保科技有限公司 | Three-layer composite polypropylene antistatic material and preparation method thereof |
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