CN115352158B - Multilayer modified polypropylene composite material capable of being extruded and molded, and preparation method and application thereof - Google Patents

Multilayer modified polypropylene composite material capable of being extruded and molded, and preparation method and application thereof Download PDF

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Publication number
CN115352158B
CN115352158B CN202210876536.4A CN202210876536A CN115352158B CN 115352158 B CN115352158 B CN 115352158B CN 202210876536 A CN202210876536 A CN 202210876536A CN 115352158 B CN115352158 B CN 115352158B
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resin
modified
polypropylene composite
modified polypropylene
10min
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CN115352158A (en
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陆佳伟
郑元俭
余文建
李保印
宋丹
王绍杰
王文博
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/10—Forming by pressure difference, e.g. vacuum
    • 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
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F25D23/062—Walls defining a cabinet
    • F25D23/064—Walls defining a cabinet formed by moulding, e.g. moulding in situ
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • 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
    • 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
    • C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a multilayer modified polypropylene composite material capable of extruding and sucking plastic, and a preparation method and application thereof, wherein the multilayer modified polypropylene composite material comprises a modified resin 1 and a modified resin 2, wherein the modified resin 1 comprises block copolymerized polypropylene resin, ternary atactic polypropylene resin, 1-polybutene resin, polycaprolactone resin and maleic anhydride grafted modified polypropylene resin; the modified resin 2 comprises block copolymerized polypropylene resin, ternary random polypropylene resin, polyether amine, glycidyl methacrylate grafted modified polypropylene resin and nylon 6 resin. And co-extruding the two materials by a single screw extruder to obtain a plate with a double-layer structure, and performing plastic suction molding on the extruded plate to obtain the refrigerator liner. The modified polypropylene refrigerator liner piece does not need surface treatment, can be well bonded with the refrigerator polyurethane heat insulation material, does not have the problem of foam layer falling in the use process, has excellent solvent resistance, and solves the problem that the HIPS refrigerator liner is easy to crack.

Description

Multilayer modified polypropylene composite material capable of being extruded and molded, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polypropylene composite materials, and relates to an extrudable plastic uptake multilayer modified polypropylene composite material, a preparation method and application thereof.
Background
The prior refrigerator liner is mostly made by extruding a plate material from HISP (high impact polystyrene) and then vacuum plastic-sucking molding. However, HIPS has become industry consensus by adopting thinner plates for plastic uptake in the process of producing and preparing the box liner because of cost control; however, the HIPS thin-wall tank container is easy to generate solvent corrosion cracking in the foaming process of the refrigerator heat-insulating material, and is easy to generate cracking due to swelling corrosion of edible oil in the normal use process, so that the rejection rate of the refrigerator with the thin-wall tank container is higher, and the resource waste is caused. The polypropylene material has excellent oil resistance, chemical corrosion resistance and stress cracking resistance, is low in price, non-toxic, low in density and low in smell in the processing process, and becomes a substitute material for a plurality of materials in the home electronics industry; however, the melting temperature of the polypropylene material is higher than that of HIPS, the softening point of the polypropylene material is very close to the melting point, the melting range is narrow, so that the polypropylene material has low melt strength and poor anti-sagging performance, and the plastic suction molding of parts with complex structures is difficult; and the polypropylene is a nonpolar material, and the prepared refrigerator liner piece is difficult to bond with the polyurethane heat preservation layer after being assembled, so that the heat preservation effect of the refrigerator is reduced, and the problem of poor bonding with the polyurethane heat preservation layer can be solved only by improving the surface polarity of the refrigerator liner after corona, plasma, flame and the like are processed on the surface of the refrigerator liner.
The patent CN112724514A adopts PP resin, polystyrene, high impact polystyrene, talcum powder and compatilizer to carry out high-temperature melt extrusion on the plate, so that the plate has better oil resistance and corrosion resistance, but has larger smell in the polystyrene processing process, the talcum powder reinforcing agent is added in the formula, so that the density of the material is increased, the weight reduction is not facilitated, and meanwhile, the bonding effect of the material and the polyurethane heat insulation layer is not evaluated.
The patent CN109438602A adopts a catalyst with wide molecular weight distribution to prepare special polypropylene which is easy to be subjected to plastic sucking, and the material has the characteristics of low processing temperature, high melt strength and good fluidity; however, the material has low impact performance at normal temperature and low temperature, and cannot meet the requirement of the low-temperature performance of the refrigerator liner.
The patent CN110669292A adopts random copolymer polypropylene with wide molecular weight distribution, ultra-low density polyethylene resin and an antioxidant, and the toughened polypropylene product is obtained by extrusion granulation of a double-screw extruder, but the low-temperature shock resistance of the material is low; the polarity of the material is low, the bonding effect with the polyurethane heat preservation layer is poor, and the material cannot be applied to refrigerator inner container parts.
Therefore, the existing plastic-absorbing modified polypropylene composite material still has a plurality of problems when being applied to refrigerator inner container parts.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a multilayer modified polypropylene composite material suitable for extrusion and plastic suction and a preparation method thereof, wherein the polypropylene composite material has high melt Cheng Kuan and melt strength and excellent heat conduction property, so that the polypropylene composite material has high preheating softening speed in the early stage of plastic suction and is beneficial to rapid molding; meanwhile, due to the multi-layer structure design, the inner layer structure has good surface polarity after being subjected to plastic suction and thinning, has good bonding effect with the polyurethane heat-insulating layer without treatment, and can be used for preparing and forming the refrigerator liner piece; the material has better low-temperature toughness and meets the performance requirement of the refrigerator liner piece in the low-temperature application process.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a multilayer modified polypropylene composite material capable of extruding and sucking plastic comprises a modified resin 1 and a modified resin 2, wherein,
the modified resin 1 comprises the following raw materials in parts by mass:
Figure BDA0003762588410000031
the modified resin 2 comprises the following raw materials in parts by mass:
Figure BDA0003762588410000032
the mass ratio of the modified resin 1 is 70-90% and the mass ratio of the modified resin 2 is 10-30% based on 100% of the total mass of the modified resin 1 and the modified resin 2.
In the invention, the melt index of the block copolymerization polypropylene resin is less than or equal to 10g/10min (230 ℃,2.16 kg); preferably, the polypropylene melt index is less than or equal to 5g/10min (230 ℃,2.16 kg).
In the invention, the melt index of the ternary random polypropylene resin is less than or equal to 20g/10min (230 ℃,2.16 kg), and the melt temperature is less than or equal to 145 ℃; preferably, the ternary random polypropylene has a melt index of 10g/10min (230 ℃ C., 2.16 kg) or less, and a melt temperature of 120 ℃ or less and 140 ℃ or less.
In the invention, the melt index of the 1-polybutene resin is less than or equal to 15g/10min (190 ℃,2.16 kg); preferably, the melt index of the 1-polybutene resin is 10g/10min (190 ℃ C., 2.16 kg) or less.
In the invention, the melt index of the polycaprolactone resin is less than or equal to 10g/10min (160 ℃ and 5 kg); preferably, the melt index of the polycaprolactone resin is less than or equal to 5g/10min (160 ℃ C., 5 kg).
In the invention, the melt index of the maleic anhydride grafted modified polypropylene resin is preferably 20-50 g/10min (230 ℃,2.16 kg), and the grafting rate of the maleic anhydride is preferably 0.5-1.5%.
In the invention, the number average molecular weight of the polyether amine is more than or equal to 3000.
In the invention, the melt index of the glycidyl methacrylate grafted modified polyethylene elastomer resin is preferably 2-10 g/10min (190 ℃,2.16 kg), the grafting rate of the glycidyl methacrylate is more than or equal to 2 percent, and the grafting rate of the glycidyl methacrylate is preferably 2-5 percent
In the invention, the melt index of the nylon 6 resin is preferably more than or equal to 2g/10min (230 ℃,2.16 kg), and preferably, the melt index of the nylon 6 resin is less than or equal to 30g/10min.
In the present invention, the lubricant is an amide-based lubricant and/or a stearic-acid-based lubricant, preferably ethylene bis-stearamide and/or zinc stearate.
In the invention, the antioxidant is any one or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
The invention also provides a preparation method of the multilayer modified polypropylene composite material, which comprises the following steps:
(1) Preparation of modified resin 1: the modified resin 1 is obtained by mixing block copolymerized polypropylene resin, ternary random polypropylene resin, 1-polybutene resin, polycaprolactone resin, maleic anhydride grafted modified polypropylene resin, lubricant and antioxidant, feeding from a main feeding port of a double-screw extruder, and performing high-temperature melting dispersion and extrusion granulation.
(2) Preparation of modified resin 2: the preparation method comprises the steps of mixing block copolymerized polypropylene resin, ternary random polypropylene resin, polyether amine, glycidyl methacrylate grafted modified polyethylene elastomer resin, nylon 6 resin, a lubricant and an antioxidant, and then placing the mixture into a double-screw extruder for melt dispersion, extruding and granulating to obtain modified resin 2.
(3) Preparation of a multilayer modified polypropylene composite material: respectively placing the prepared modified resin 1 and modified resin 2 into two single-screw extruders for plasticizing, and casting through a coextrusion die head to prepare a double-layer plate, wherein the mass ratio of the modified resin 1 is preferably 70-90%, and the mass ratio of the modified resin 2 is preferably 10-30%; the prepared plate is subjected to pretreatment at 120-140 ℃ for 5-20 min and then is rapidly cooled, and is subjected to plastic suction molding after being placed for 4-8 h, so that a well-molded refrigerator liner product can be obtained, and the product can have better adhesiveness with polyurethane foam without surface treatment when being assembled, and has excellent solvent cracking resistance.
In the invention, the length-diameter ratio of the screw of the double screw extruder in the steps (1) and (2) is (40-52), the rotating speed of the screw is 100-500r/min, and the extrusion temperature is 220-240 ℃.
In the invention, the length-diameter ratio of the screw of the single screw extruder in the step (3) is (25-35): 1, the rotating speed of the screw is 100-500r/min, and the extrusion temperature is 220-240 ℃.
The multilayer modified polypropylene composite material provided by the invention can be used for preparing a thin-wall refrigerator liner with excellent solvent resistance and corrosion cracking resistance, and has good cohesiveness with polyurethane foam materials.
In the present invention, the modified resin 2 is contacted with a polyurethane foam.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the modified resin 1 in the invention uses resin materials with different melting temperature ranges, so that the modified resin has a wider melting range, the low-melting-point part material provides plasticizing flow property, and the high-melting-point part material provides skeleton supporting function, so that the modified resin has excellent anti-sagging property in the extrusion and plastic sucking processes; the modified resin 1 is prepared by reacting polycaprolactone resin with maleic anhydride grafted modified polypropylene resin to form a comb-shaped polymer, which is favorable for the compatibility and dispersibility of the polycaprolactone resin in matrix resin, and the polycaprolactone resin has a lower melting temperature and higher thermal conductivity than polypropylene, so that the polycaprolactone resin is favorable for the conduction of heat in the matrix resin in the plasticizing process, and can be softened and molded in a plastic suction manner in a shorter time.
2. The modified resin 2 in the invention uses polyether amine, nylon 6 resin and glycidyl methacrylate grafted modified polyethylene elastomer resin to carry out grafting reaction, wherein the nylon 6 resin and the polyether amine have better polarity, and in the plastic sucking process, the hydrogen bond between the polyether amine chain segment of the grafting reaction and the nylon 6 resin forms a heat conduction network, so that the heat conduction network is easier to absorb heat and plasticize; meanwhile, nylon 6 and polyether amine chain segments are easy to migrate to the surface layer of the material, and can react with isocyanate groups in the polyurethane foaming process, so that the bonding effect of the refrigerator liner piece and the polyurethane foaming material is improved.
3. The double-layer plate for preparing the refrigerator liner piece is prepared by co-extrusion casting of the modified resin 1 and the modified resin 2 through two single-screw extruders, wherein the two layers of the double-layer plate are made of resin materials with different melting temperature ranges, so that melting ranges suitable for plastic suction are obtained, and the resin materials with the two layers of the double-layer plate have excellent room temperature and low temperature impact performance and meet the requirement of the refrigerator liner on low temperature performance; wherein the area of the board contacted with the polyurethane foaming material uses the modified resin 2, so that the consumption of PA6 and polyetheramine in the whole board is reduced, the cost can be reduced, and in the plastic uptake process of the refrigerator liner, the board can be thinned, so that the PA6 resin and polyetheramine chain segments are more easily migrated to the surface, and then are subjected to chemical reaction with the polyurethane foaming material, the bonding effect of the foaming material and the refrigerator liner is improved, and the practical application requirement of the refrigerator is met.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples. The raw materials used in examples and comparative examples were commercially available raw materials unless otherwise specified.
The device and main raw material sources used in the examples and comparative examples of the present invention are as follows:
twin screw extruder: model CTE-35, screw aspect ratio 48:1, keplon (Nanj) mechanical Co., ltd.
Single screw coextrusion apparatus: model HRJSJ-35, screw length-diameter ratio of 28:1, sea Ruija precision extrusion machinery Co., ltd.
Block copolymerized polypropylene resin: k8303, melt index 3g/10min (230 ℃,2.16 kg), china petrochemical company;
ternary random polypropylene resin: FL7632L, melt index 7g/10min (230 ℃,2.16 kg), china petrochemical company;
1-polybutene resin: PB 4235-1 having a melt index of 0.6g/10min (190 ℃,2.16 kg), liandbarsel
Polycaprolactone resin: esun 1000C with a melt index of 7g/10min (160 ℃ C., 5 kg), shenzhen Guanghua Wenyujin Co., ltd
Maleic anhydride grafted modified polypropylene resin: GPM200B, optical Co., ltd, having a melt index of 30 to 50g/10min (230 ℃ C., 2.16 kg)
Polyetheramine: d4000, number average molecular weight 4000, red Baoli group Co., ltd
Glycidyl methacrylate graft modified polyethylene elastomer resin: e533, 3g/10min melt index (190 ℃,2.16 kg), 3% glycidyl methacrylate grafting, available from light Co., ltd.)
Nylon 6 resin: m2400 melt index 26g/10min (230 ℃,2.16 kg), new Endometacin Co., ltd
An antioxidant: an antioxidant 1010 belonging to the class of hindered phenol catalysts, BASF (BASF, china limited);
an antioxidant: an antioxidant 168 belonging to the phosphite group catalyst, BASF (BASF, BASF chinese limited);
the performance characterization method of the multilayer modified polypropylene composite material comprises the following steps:
flexural modulus: GB/T9341-2008;
tensile strength: GB/T1040.2-2006;
cantilever impact strength: GB/T1843-2008;
the solvent resistance testing method comprises the following steps: the tensile bars were fixed to an ESCR mold with a bending strain of 2%, placed in a pressure-resistant corrosion tank containing a foaming agent cyclopentane liquid, kept at a temperature of 40±1 ℃ for 4 hours, and after the corrosion was completed, the bars were taken out and placed for 24 hours for tensile strength testing.
The method for testing the bonding effect of the polyurethane foaming material comprises the following steps: placing the refrigerator inner container part in a foaming mold, adding polyol, isocyanate and foaming agent for foaming, taking out the inner container part after the foaming is finished, placing for 24 hours, cutting a 100 mm-100 m plane of the inner container part by a knife, performing peeling test, and checking the bonding condition of polyurethane foaming materials on the surface of the material.
The solvent resistance test method for the liner part of the plastic uptake refrigerator comprises the following steps: the molded article was cut into 100mm panels and placed in cyclopentane solvent for 1h, and the appearance of the panels was observed.
Examples 1 to 4 (i.e., S1 to 4) and comparative examples 1 to 5 (i.e., D1 to 5), the preparation of the modified resin 1 was carried out according to the respective raw materials and amounts shown in Table 1;
example 1
The preparation method comprises the following steps: weighing 60 parts of K8303, 17 parts of FL7632L, 10 parts of PB 4235-1, 10 parts of Esun 1000C, 2 parts of GPM-200B, 0.6 part of zinc stearate, 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 168 according to the weight ratio, mixing for 3-10min, feeding from a main feeding port of a double-screw extruder, performing high-temperature melting dispersion, extruding and granulating to obtain modified resin 1.
Examples 2 to 4
Modified resin 1 was prepared according to the respective raw materials and amounts shown in Table 1, and the specific preparation method was the same as that of example 1.
Comparative examples 1 to 5
Modified resin 1 was prepared according to the respective raw materials and amounts shown in Table 1, and the specific preparation method was the same as that of example 1.
TABLE 1 examples 1-4 and comparative examples 1-5 raw materials and amounts thereof
Wt％ S1 S2 S3 S4 D1 D2 D3 D4 D5
K8303/wt％ 60 49 40 42 52 44 87 37 67
FL7632L/wt％ 17 10 14 40 40 40 0 50 0
PB 4235-1/wt％ 10 20 5 5 5 5 0 0 20
Esun 1000C/wt％ 10 15 30 10 0 10 10 10 10
GPM-200B/wt％ 2 5 10 2 2 0 2 2 2
Zinc stearate in wt% 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
1010/wt％ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
168/wt％ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Examples 5 to 8 (i.e., S5 to 8) and comparative examples 6 to 9 (i.e., D6 to 9), the preparation of the modified resin 2 was carried out according to the respective raw materials and amounts shown in Table 2;
example 5
The preparation method comprises the following steps: weighing 40 parts of K8303, 19 parts of FL7632L, 5 parts of D4000, 15 parts of E533, 20 parts of M2400, 0.6 part of zinc stearate, 0.2 part of antioxidant 1010 and 0.2 part of antioxidant 168 according to the weight ratio, putting the materials into a high-speed mixer for mixing for 3-10min, feeding the materials from a main feeding port of a double-screw extruder, and carrying out high-temperature melting dispersion and extrusion granulation to obtain the modified resin 2.
Examples 6 to 8
Modified resin 2 was prepared according to the respective raw materials and amounts shown in Table 2, and the specific preparation method was the same as in example 5.
Comparative examples 5 to 8
Modified resin 2 was prepared according to the respective raw materials and amounts shown in Table 2, and the specific preparation method was the same as in example 5.
TABLE 2 raw materials for examples 5 to 8 and comparative examples 6 to 9 and amounts thereof
Wt％ S5 S6 S7 S8 D6 D7 D8 D9
K8303/wt％ 40 57 70 64 84 69 64 69
FL7632L/wt％ 19 16 10 20 0 20 20 15
D4000/wt％ 5 3 2 5 5 0 5 5
E533/wt％ 15 10 5 5 5 5 0 10
M2400/wt％ 20 13 12 5 5 5 10 0
Zinc stearate in wt% 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6
1010/wt％ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
168/wt％ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
TABLE 3 results of performance testing of examples 1-4 and comparative examples 1-5 and HIPS
Figure BDA0003762588410000101
TABLE 4 results of performance testing of examples 5-8 and comparative examples 6-9 and HIPS
Figure BDA0003762588410000111
From the test data in tables 3 and 4, it can be seen that the solvent resistance of the modified polypropylene material is significantly better than that of HIPS material.
Example 9
Respectively placing 80 parts of S1 and 20 parts of S5 in two single screw extruders for plasticizing, preparing a double-layer plate through casting by a coextrusion extrusion die head, carrying out high-temperature pretreatment on the prepared plate at 120 ℃ for 10min, then rapidly cooling, placing for 4h, and then carrying out plastic suction molding to obtain a refrigerator liner part, carrying out foaming adhesion test on the part by using a double-component polyurethane foaming material, placing for 24h after foaming is finished, cutting a 100mm x 100m plane by using a knife on the liner part, carrying out peeling test, and checking the adhesion condition of the polyurethane foaming material on the surface of the material. The molded article was cut into 100mm panels, and after 1 hour of placing in a cyclopentane solvent, the appearance of the panels was observed and the solvent resistance of the material was evaluated.
Examples 10 to 12
Refrigerator liners were prepared according to the respective raw materials and amounts shown in table 5, and the specific preparation method is referred to in example 9.
Comparative examples 13 to 19
Refrigerator liners were prepared according to the respective raw materials and amounts shown in table 5, and the specific preparation method is referred to in example 9.
TABLE 5 results of Performance test for examples 9-12 and comparative examples 13-19
Figure BDA0003762588410000112
Figure BDA0003762588410000121
It can be found from table 5 that, in examples 9 to 12, resin materials with different melting temperature ranges are used, so that the resin materials have a wider melting range, the low-melting-point part material provides plasticizing fluidity, the high-melting-point part material provides skeleton supporting function, the prepared plate is rapidly cooled after being pretreated at a high temperature for 10min, and unmelted crystals are induced to form perfect crystals with higher melting temperature by taking the perfect crystals as crystal nuclei in the high-temperature pretreatment process, so that only the low-melting-point part is melted in the preheating process before plastic suction, and the perfect crystals with high melting point can prevent the plate from having a suction breaking problem in the plastic suction process, thereby ensuring that the thickness of the box liner part is uniform and the plastic suction effect is better; meanwhile, the polycaprolactone resin and the maleic anhydride grafted modified polypropylene resin are used for reacting to form a comb-shaped polymer, so that the compatibility and the dispersibility of the polycaprolactone resin in the matrix resin are facilitated, and the polycaprolactone resin is low in melting temperature and higher in thermal conductivity than the polypropylene, so that the heat conduction in the matrix resin is facilitated in the plasticizing process, and the polycaprolactone resin can be softened and molded in a plastic suction manner in a short time.
The plate prepared in comparative example 13 was not subjected to high temperature pretreatment, and the thickness of the product was not uniform during the suction molding process. The modified resin 1 of comparative example 14 was not used with polycaprolactone, and the modified resin 1 of comparative example 15 was not added with a maleic anhydride-grafted modified polypropylene resin that was grafted by the reaction of polycaprolactone, resulting in poor preheating plasticizing effect before plastic suction and poor molding of the molded article. The modified resin 2 in comparative example 14 was not added with the low melting point resin FL7632L, so that it could not be effectively stretched and thinned during the plastic suction process, and the PA6 resin and the polyether amine segment could not be well migrated to the surface, resulting in poor adhesion effect with polyurethane foam. The polyether amine is not added in the comparative example 15, so that the modified resin 2 cannot effectively react and graft with the foaming material after the plastic uptake is thinned, and the bonding effect of the modified resin and the polyurethane foaming material is poor.
The modified resin 1 of comparative example 16 was not added with the low melting point resin FL7632L, PB 4235-1, the modified resin 1 of comparative example 17 was not added with the low melting point resin PB 4235-1, and the modified resin 1 of comparative example 18 was not added with the low melting point resin FL7632L, resulting in poor preheating plasticizing effect before plastic suction and poor plastic suction molding of the article. The modified resin 2 of comparative example 16 was not added with the elastomer compatibilizer E533, so that the dispersion compatibility of nylon M2400 and polyetheramine D4000 was poor, resulting in poor adhesion with polyurethane foam. The modified resin 2 of comparative examples 17 and 18 was poor in adhesion to polyurethane foam because of the absence of nylon M2400.
The HIPS material of the comparative example 19 is swelled and cracked, and the thin-wall tank containers prepared by the materials of the examples 9-12 and the comparative examples 13-19 have excellent solvent resistance, so that the problems that the thin-wall tank container is easy to crack due to solvent corrosion in the foaming process of the refrigerator heat insulation material and is easy to crack due to swelling and corrosion of edible oil in the normal use process can be effectively solved.
The foregoing description of the embodiments is provided to facilitate the understanding and appreciation of the invention by those skilled in the art. Various modifications to the embodiments will be readily apparent to those skilled in the art, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (22)

1. The multilayer modified polypropylene composite material capable of being subjected to extrusion and plastic suction comprises a modified resin 1 and a modified resin 2, wherein the modified resin 1 comprises the following raw materials in parts by weight:
40-70 parts of block copolymerized polypropylene resin,
10-40 parts of ternary random polypropylene resin,
5-20 parts of 1-polybutene resin,
10-30 parts of polycaprolactone resin,
2-10 parts of maleic anhydride grafted modified polypropylene resin,
0.2 to 1 part of lubricant,
0.2-1 part of antioxidant;
the modified resin 2 comprises the following raw materials in parts by mass:
40-70 parts of block copolymerized polypropylene resin,
10-20 parts of ternary random polypropylene resin,
2-5 parts of polyether amine,
5-15 parts of glycidyl methacrylate grafted modified polyethylene elastomer resin,
5-20 parts of nylon 6 resin,
0.2 to 1 part of lubricant,
0.2-1 part of antioxidant;
based on the total mass of the modified resin 1 and the modified resin 2 being 100%, the mass ratio of the modified resin 1 is 70-90%, and the mass ratio of the modified resin 2 is 10-30%;
the multilayer modified polypropylene composite material is characterized in that modified resin 1 and modified resin 2 are respectively placed in two extruders for plasticizing, a double-layer plate is prepared through casting of a coextrusion die head, and the prepared plate is cooled and subjected to plastic suction molding after being subjected to high-temperature pretreatment for 5-20 min at 120-140 ℃.
2. The multilayer modified polypropylene composite according to claim 1, wherein said block copolymerized polypropylene resin has a melt index of 10g/10min or less under test conditions of 2.16kg at 230 ℃.
3. The multilayer modified polypropylene composite according to claim 2, wherein the melt index of the block copolymerized polypropylene resin is 5g/10min or less under a test condition of 2.16kg at 230 ℃.
4. The multilayer modified polypropylene composite according to claim 1, wherein the melt index of the ternary random polypropylene resin is 20g/10min or less and the melt temperature is 145 ℃ or less under the test condition of 230 ℃ and 2.16 kg.
5. The multilayer modified polypropylene composite according to claim 4, wherein the melt index of the ternary random polypropylene resin is 10g/10min or less, and the melting temperature is 120 ℃ or less and 140 ℃ or less under the test condition of 230 ℃ and 2.16 kg.
6. The multi-layer modified polypropylene composite according to claim 1, wherein said 1-polybutene resin has a melt index of 15g/10min or less under a test condition of 2.16kg at 190 ℃.
7. The multi-layer modified polypropylene composite according to claim 6, wherein said 1-polybutene resin has a melt index of 10g/10min or less under test conditions of 2.16kg at 190 ℃.
8. The multi-layer modified polypropylene composite according to claim 1, wherein said polycaprolactone resin has a melt index of 10g/10min or less under test conditions of 5kg at 160 ℃.
9. The multi-layer modified polypropylene composite according to claim 8, wherein said polycaprolactone resin has a melt index of 5g/10min or less under a test condition of 5kg at 160 ℃.
10. The multilayer modified polypropylene composite according to claim 1, wherein the melt index of the maleic anhydride grafted modified polypropylene resin is 20-50 g/10min and the maleic anhydride grafting ratio is 0.5-1.5% under the test condition of 2.16kg at 230 ℃.
11. The multilayer modified polypropylene composite according to claim 1, wherein the polyetheramine has a number average molecular weight of not less than 3000.
12. The multilayer modified polypropylene composite material according to claim 1, wherein the melt index of the glycidyl methacrylate grafted modified polyethylene elastomer resin is 2-10 g/10min under the test condition of 190 ℃ and 2.16kg, and the grafting rate of the glycidyl methacrylate is more than or equal to 2%.
13. The multilayer modified polypropylene composite according to claim 12, wherein the glycidyl methacrylate grafting ratio is 2-5%.
14. The multi-layer modified polypropylene composite according to claim 1, wherein said nylon 6 resin has a melt index of > 2g/10min under test conditions of 2.16kg at 230 ℃.
15. The multi-layer modified polypropylene composite according to claim 14, wherein said nylon 6 resin has a melt index of 30g/10min or less.
16. The multi-layer modified polypropylene composite according to claim 1, wherein said lubricant is an amide-based lubricant and/or a stearic acid-based lubricant, respectively.
17. The multi-layer modified polypropylene composite according to claim 16, wherein said lubricant is ethylene bis stearamide and/or zinc stearate.
18. The multi-layer modified polypropylene composite according to claim 1, wherein said antioxidant is any one or more of hindered phenol type antioxidants, phosphite type antioxidants and thio ester type antioxidants.
19. A method of preparing a multilayer modified polypropylene composite as claimed in any one of claims 1 to 18, comprising the steps of:
(1) Preparation of modified resin 1: mixing block copolymerized polypropylene resin, ternary random polypropylene resin, 1-polybutene resin, polycaprolactone resin, maleic anhydride grafted modified polypropylene resin, lubricant and antioxidant, feeding from a main feeding port of a double-screw extruder, and performing high-temperature melting dispersion, extrusion granulation to obtain modified resin 1;
(2) Preparation of modified resin 2: mixing block copolymerized polypropylene resin, ternary random polypropylene resin, polyether amine, glycidyl methacrylate grafted modified polyethylene elastomer resin, nylon 6 resin, a lubricant and an antioxidant, and then placing the mixture into a double-screw extruder for melt dispersion, extruding and granulating to obtain modified resin 2;
(3) Preparation of a multilayer modified polypropylene composite material: respectively placing the modified resin 1 and the modified resin 2 in two extruders for plasticizing, preparing a double-layer plate through casting by a co-extrusion die head, and cooling and carrying out plastic suction molding after carrying out high-temperature pretreatment on the prepared plate for 5-20 min at 120-140 ℃.
20. The process according to claim 19, wherein the twin-screw extruder of steps (1) and (2) has a screw aspect ratio of (40-52) of 1, a screw rotation speed of 100-500r/min and an extrusion temperature of 220-240 ℃.
21. The process of claim 19, wherein the extruder of step (3) has a screw aspect ratio of (25-35): 1, a screw speed of 100-500r/min, and an extrusion temperature of 220-240 ℃.
22. A thin-walled refrigerator liner prepared from the multi-layer modified polypropylene composite material according to any one of claims 1 to 18 or the polypropylene composite material prepared by the preparation method according to any one of claims 19 to 21, wherein the modified resin 2 is in contact with polyurethane foam.
CN202210876536.4A 2022-07-25 2022-07-25 Multilayer modified polypropylene composite material capable of being extruded and molded, and preparation method and application thereof Active CN115352158B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004330422A (en) * 2003-04-30 2004-11-25 Kuraray Co Ltd Laminate
JP2008273147A (en) * 2007-05-07 2008-11-13 Daicel Pack Systems Ltd Laminated sheet for container
CN114736460A (en) * 2022-04-27 2022-07-12 海信（山东）冰箱有限公司 Refrigerator liner material, preparation method thereof and refrigerator liner

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004330422A (en) * 2003-04-30 2004-11-25 Kuraray Co Ltd Laminate
JP2008273147A (en) * 2007-05-07 2008-11-13 Daicel Pack Systems Ltd Laminated sheet for container
CN114736460A (en) * 2022-04-27 2022-07-12 海信（山东）冰箱有限公司 Refrigerator liner material, preparation method thereof and refrigerator liner

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