CN113563670A - High-melt-strength polybutylene bead as well as preparation method and application thereof - Google Patents

High-melt-strength polybutylene bead as well as preparation method and application thereof Download PDF

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Publication number
CN113563670A
CN113563670A CN202110829976.XA CN202110829976A CN113563670A CN 113563670 A CN113563670 A CN 113563670A CN 202110829976 A CN202110829976 A CN 202110829976A CN 113563670 A CN113563670 A CN 113563670A
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melt strength
high melt
butene
polybutene
poly
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Inventor
袁文博
王世斌
史来勇
赵明雷
杨秀珍
刘莉雪
冷栋梁
王耀伟
栾波
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Shandong Chambroad Petrochemicals Co Ltd
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Shandong Chambroad Petrochemicals Co Ltd
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    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • 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
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—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
    • C08J2351/00—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
    • C08J2351/06—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
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    • 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
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    • 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
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    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/36—Silica

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Abstract

The invention provides high melt strength polybutylene beads and a preparation method and application thereof; the high melt strength polybutylene bead is prepared from the following raw materials: 100 parts by weight of a base resin; 0.1 to 1 weight part of antioxidant; the base resin is selected from one or more of poly-1-butene, poly-1-butene alloy, poly-1-butene random copolymer, graft-modified high melt strength material containing poly-1-butene; the melt flow index of the base resin is 0.1g/10 min-2 g/10 min. Compared with the prior art, the high melt strength polybutylene bead provided by the invention has the advantages of wider molecular weight distribution, excellent mechanical property and suitability for foaming; the further prepared foaming material has excellent high-strength anti-retraction property, shock absorption and energy absorption property, low temperature resistance, chemical corrosion resistance and good environment friendliness, is suitable for various foaming forming modes, has the advantages of low cost, short period, controllable density and the like, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.

Description

High-melt-strength polybutylene bead as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of high-molecular foaming materials, in particular to polybutylene beads with high melt strength and a preparation method and application thereof.
Background
The polymer foam material has low density, high specific strength, sound insulation, heat insulation and other barrier properties and excellent energy absorption characteristics, so that the market consumption of the polymer foam material in the global range is continuously increased since the invention of the polymer foam material in the 40 th 20 th century, which reflects that the production of the polymer foam material becomes an industry affecting various aspects of our lives and becomes an important industrial material in the 21 st century. With the emergence of novel processing theory and production technology, the application field of polymer foaming materials is continuously expanded, for example, microcellular foam plastics can be used in a plurality of fields such as transportation, building, packaging, daily necessities and aerospace, and have infinite development potential, wherein the polyolefin foaming materials have good development prospects.
The polyolefin foam material has more applications and is widely researched by polyethylene and polypropylene, wherein the polyethylene foam plastic has wider application, but the mechanical property and the heat resistance of the polyethylene foam plastic are not ideal; the polypropylene foaming material has the advantages of good mechanical property, excellent energy absorption and low price, but has the biggest defects of low melt strength, easy breakage, collapse and combination of foam pores formed in the foaming process, and the problems of poor quality, uneven pore size distribution, low foaming multiplying power and the like of the foaming material. Therefore, a new olefin material with simple production process and excellent performance still needs to be found as a novel foaming material to meet the continuously improved requirements of people.
Disclosure of Invention
In view of the above, the present invention provides a high melt strength polybutene bead, and a preparation method and applications thereof, and the high melt strength polybutene bead provided by the present invention has the advantages of wide molecular weight distribution, excellent mechanical properties, and suitability for foaming; the further prepared foaming material has excellent high-strength anti-retraction property, shock absorption and energy absorption property, low temperature resistance, chemical corrosion resistance and good environment friendliness, is suitable for various foaming forming modes, has the advantages of low cost, short period, controllable density and the like, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.
The invention provides high-melt-strength polybutylene beads, which are prepared from the following raw materials:
100 parts by weight of a base resin;
0.1 to 1 weight part of antioxidant;
the base resin is selected from one or more of poly-1-butene, poly-1-butene alloy, poly-1-butene random copolymer, graft-modified high melt strength material containing poly-1-butene; the melt flow index of the base resin is 0.1g/10 min-2 g/10 min.
Preferably, the antioxidant is selected from one or more of hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants.
Preferably, the high melt strength polybutene beads further comprise:
0.1 to 5 parts by weight of nucleating agent;
0.1 to 50 parts by weight of a graft monomer;
0.01-20 parts by weight of processing aid;
0.1 to 1 weight portion of initiator.
Preferably, the nucleating agent is selected from one or more of nano silica, talcum powder, carbon black and nano calcium carbonate.
Preferably, the grafting monomer is selected from one or more of cardanol, PETA, styrene and 1-octene.
Preferably, the processing aid is selected from one or more of calcium stearate, magnesium stearate and zinc stearate.
Preferably, the initiator is selected from one or more of benzoyl peroxide, dicumyl peroxide, 2, 3-dimethyl-2, 3-diphenylbutane, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane and di-tert-butylperoxycumene.
The invention also provides a preparation method of the high melt strength polybutylene bead, which comprises the following steps:
a) the raw materials are uniformly mixed according to the component amount, added into a double-screw extruder to be extruded and pulled into strips, and then sequentially cooled, air-cooled to remove water and cut into granules, so that the high-melt-strength polybutene beads are obtained.
Preferably, the double-screw extruder in the step a) has 12 sections from the feed opening to the heating zone of the head, and the sections are sequentially set to be 160-170 ℃, 175-185 ℃, 190-195 ℃, 190-220 ℃, 190-210 ℃, the screw rotation speed is 100-300 r/min, and the feeding rotation speed is 1-10 r/min.
The invention also provides an application of the resin particle material in preparing a foaming material, wherein the resin particle material is the high-melt-strength polybutylene bead in the technical scheme.
The invention provides high melt strength polybutylene beads and a preparation method and application thereof; the high melt strength polybutylene bead is prepared from the following raw materials: 100 parts by weight of a base resin; 0.1 to 1 weight part of antioxidant; the base resin is selected from one or more of poly-1-butene, poly-1-butene alloy, poly-1-butene random copolymer, graft-modified high melt strength material containing poly-1-butene; the melt flow index of the base resin is 0.1g/10 min-2 g/10 min. Compared with the prior art, the high melt strength polybutylene bead provided by the invention adopts specific content components, so that the integral better interaction is realized, the obtained high melt strength polybutylene bead has wider molecular weight distribution and excellent mechanical property, and is suitable for foaming; the further prepared foaming material has excellent high-strength anti-retraction property, shock absorption and energy absorption property, low temperature resistance, chemical corrosion resistance and good environment friendliness, is suitable for various foaming forming modes, has the advantages of low cost, short period, controllable density and the like, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.
In addition, the preparation method provided by the invention is simple in process, easy in condition control and suitable for large-scale industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of high melt strength polybutene beads provided in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of high melt strength polybutene beads provided in example 2 of the present invention;
FIG. 3 is a scanning electron micrograph of high melt strength polybutene beads provided in example 3 of the present invention;
fig. 4 is a scanning electron microscope image of the high melt strength polybutene beads provided by example 4 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides high-melt-strength polybutylene beads, which are prepared from the following raw materials:
100 parts by weight of a base resin;
0.1 to 1 weight part of antioxidant;
the base resin is selected from one or more of poly-1-butene, poly-1-butene alloy, poly-1-butene random copolymer, graft-modified high melt strength material containing poly-1-butene; the melt flow index of the base resin is 0.1g/10 min-2 g/10 min.
In the present invention, the High Melt Strength Polybutene Beads (HMSPB) are modified resin particles containing 1-butene. The poly-1-butene has good physical and mechanical properties, outstanding creep resistance, chemical resistance, low temperature resistance, environmental stress cracking resistance, good mechanical strength and high toughness; the yield value, tensile strength and impact strength of the LDPE are respectively 2 times, 6-10 times and 3-4 times of that of LDPE. Compared with other polyolefins, polybutene-1 has the best stress cracking resistance, higher creep resistance than polyethylene and polypropylene, and outstanding creep resistance under stress not exceeding the yield point is maintained up to 80 ℃. The resin material containing the poly-1-butene is combined with different grafting monomers, has the characteristics of high molecular weight and wide molecular weight distribution, so that the melt strength is high, the foaming temperature interval is wide, and the closed-cell foaming beads with uniform and compact foam holes and adjustable foam hole diameters can be prepared. At present, the utilization rate of poly-1-butene in China is low, and the poly-1-butene is mainly applied to the field of plastic pipes for conveying cold water and hot water. The foaming material made of the grafting particles containing the poly-1-butylene has excellent high-strength retraction resistance, shock absorption performance, low temperature resistance and chemical corrosion resistance, is suitable for various foaming forming modes, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.
In the present invention, the base resin is selected from one or more of polybutene-1, polybutene-1 alloys (in which polybutene-1 is partially blocked with other polyolefin components in view of the microstructure of the alloy), polybutene-1 random copolymers, graft-modified high melt strength materials containing polybutene-1, preferably from one or more of polybutene-1, polybutene-1 random copolymers (such as butene-1 copolymer resin (propane-butadiene copolymer), and graft-modified high melt strength materials containing polybutene-1 (such as graft-modified butene-containing resins) in which other polyolefin components are introduced to effectively increase the crystal transformation rate, impact resistance, etc. of polybutene). In the invention, the 1-butene content in the poly-1-butene alloy is preferably 30-98%, and the content of corresponding alpha-olefin (one or more selected from propylene, ethylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene) is 70-2%; the content of 1-butene in the poly-1-butene random copolymer is preferably 30-95%, and the content of corresponding alpha-olefin (one or more selected from propylene, ethylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene) is 70-5%; the content of the 1-butene in the graft modified high-melt-strength material containing the poly-1-butene is preferably 30-96%, the content of the corresponding alpha-olefin is 69-2%, and the content of the graft monomer is 1-2%.
In the present invention, the base resin has a melt flow index (190 ℃ C., 2.16Kg) of 0.1g/10min to 2g/10min, preferably 0.5g/10min to 2g/10 min. The invention takes the resin material containing poly-1-butylene as the raw material, the melt flow index (190 ℃, 2.16Kg) is 0.1g/10 min-2 g/10min, the melt strength is high, and the melting peak is wider. The source of the base resin is not particularly limited in the present invention, and commercially available products or self-products known to those skilled in the art may be used. If the poly-1-butene is prepared by a kettle batch method, the molecular weight distribution Mw/Mn is 2-10, and the melt flow index (190 ℃, 2.16Kg) is 0.1-2 g/10 min); the poly-1-butene alloy is prepared by a kettle-type two-step method, the molecular weight distribution Mw/Mn of the poly-1-butene alloy is 2-10, and the melt flow index (190 ℃, 2.16Kg) is 0.1-2 g/10 min); the poly-1-butene copolymer is prepared by kettle type one-step copolymerization, the molecular weight distribution Mw/Mn is 2-10, and the melt flow index (190 ℃, 2.16Kg) is 0.1-2 g/10 min); the graft-modified high-melt-strength material containing the poly-1-butene is prepared by taking polybutylene alloy powder as base resin, taking different monomers as grafts and adding other auxiliaries through a melt grafting method, wherein the molecular weight distribution Mw/Mn is 2-10, and the melt flow index (190 ℃, 2.16Kg) is 0.1-2 g/10 min).
In the present invention, the base resin is preferably dried in a plastic mixing dryer before use.
In the present invention, the antioxidant is preferably selected from one or more of hindered phenol-based antioxidants, phosphite-based antioxidants and thioester-based antioxidants. The source of the antioxidant is not particularly limited in the present invention, and commercially available products of the above hindered phenol type antioxidants, phosphite type antioxidants and thioester type antioxidants known to those skilled in the art may be used. In a preferred embodiment of the invention, the antioxidant is a mixture of 1: 1 antioxidant 1010 and antioxidant 168.
In a preferred embodiment of the present invention, the base resin is a random copolymer of poly-1-butene and a graft-modified high melt strength material comprising poly-1-butene; the high melt strength polybutylene bead is prepared from a base resin and an antioxidant; wherein the mass ratio of the base resin to the antioxidant is 100: (0.1 to 1), preferably 100: (0.2-0.4).
In another preferred embodiment of the present invention, the base resin is poly-1-butene or a poly-1-butene random copolymer; the high melt strength polybutylene bead is prepared from raw materials including a base resin and an antioxidant; preferably, the method further comprises the following steps:
0.1 to 5 parts by weight of nucleating agent;
0.1 to 50 parts by weight of a graft monomer;
0.01-20 parts by weight of processing aid;
0.1 to 1 weight part of initiator;
on this basis, the high melt strength polybutene beads comprise:
100 parts by weight of a base resin;
0.1 to 1 weight part of antioxidant;
0.1 to 5 parts by weight of nucleating agent;
0.1 to 50 parts by weight of a graft monomer;
0.01-20 parts by weight of processing aid;
0.1 to 1 weight part of initiator;
preferably:
100 parts by weight of a base resin;
0.1 to 0.2 weight portions of antioxidant;
0.1 to 0.3 weight portions of nucleating agent;
2.5 to 3 parts by weight of a grafting monomer;
0.04 to 0.06 weight portion of processing aid;
0.15 to 0.25 weight portion of initiator.
In the present invention, the nucleating agent is preferably selected from one or more of nano silica, talc, carbon black and nano calcium carbonate, and more preferably nano silica. The source of the nucleating agent is not particularly limited in the present invention, and commercially available products of the above-mentioned nano silica, talc, carbon black and nano calcium carbonate, which are well known to those skilled in the art, may be used. In the invention, the nucleating agent is preferably dried in a vacuum drying oven at 50-700 ℃ for 10-14 h before use.
In the present invention, the grafting monomer is preferably selected from one or more of cardanol, PETA, styrene and 1-octene, more preferably three of cardanol, PETA, styrene and 1-octene. In a preferred embodiment of the present invention, the grafting monomers are present in a mass ratio of 2: 0.2: 0.5 of cardanol, PETA and styrene; in another preferred embodiment of the present invention, the grafting monomers are present in a mass ratio of 2: 0.2: 0.5 of 1-octene, PETA and styrene. The source of the graft monomer is not particularly limited in the present invention, and commercially available products of cardanol, PETA, styrene and 1-octene described above, which are well known to those skilled in the art, may be used.
In the present invention, the processing aid is preferably selected from one or more of calcium stearate, magnesium stearate and zinc stearate, and more preferably calcium stearate. The source of the processing aid is not particularly limited in the present invention, and commercially available products of the above calcium stearate, magnesium stearate and zinc stearate, which are well known to those skilled in the art, may be used. In the invention, the processing aid is preferably dried in a vacuum drying oven at 50-700 ℃ for 10-14 h before use.
In the present invention, the initiator is preferably selected from one or more of benzoyl peroxide, dicumyl peroxide, 2, 3-dimethyl-2, 3-diphenylbutane, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane and di-tert-butylperoxyisopropyl benzene, and more preferably is di-tert-butylperoxyisopropyl benzene (initiator BIPB) or 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane (initiator 101). The source of the initiator is not particularly limited in the present invention, and commercially available products of the above-mentioned benzoyl peroxide, dicumyl peroxide, 2, 3-dimethyl-2, 3-diphenylbutane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane and di-t-butylperoxyisopropyl benzene known to those skilled in the art can be used.
The high melt strength polybutylene bead provided by the invention adopts specific content components, so that the integral better interaction is realized, the obtained high melt strength polybutylene bead has wider molecular weight distribution and excellent mechanical property, and is suitable for foaming; the further prepared foaming material has excellent high-strength anti-retraction property, shock absorption and energy absorption property, low temperature resistance, chemical corrosion resistance and good environment friendliness, is suitable for various foaming forming modes, has the advantages of low cost, short period, controllable density and the like, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.
The invention also provides a preparation method of the high melt strength polybutylene bead, which comprises the following steps:
a) the raw materials are uniformly mixed according to the component amount, added into a double-screw extruder to be extruded and pulled into strips, and then sequentially cooled, air-cooled to remove water and cut into granules, so that the high-melt-strength polybutene beads are obtained.
In the invention, the raw materials are the raw materials in the technical scheme, and the component dosage is the component dosage defined in the technical scheme; the present invention will not be described herein.
In the invention, the raw materials are uniformly mixed according to the using amount of the components, and the raw materials are preferably stirred by a high-speed mixer well known by a person skilled in the art; the stirring time is preferably 4 to 6min, and more preferably 5 min.
In the invention, the heating zone of the double-screw extruder from the feed opening to the machine head preferably has 12 sections, which are sequentially set to 160-170 ℃, 175-185 ℃, 190-195 ℃, 190-220 ℃, 190-210 ℃, more preferably set to 165 ℃, 180 ℃, 190-195 ℃, 190-220 ℃, 190-210 ℃ and 190-210 ℃; the screw rotation speed is preferably 100 r/min-300 r/min, more preferably 130 r/min-260 r/min, and the feeding rotation speed is preferably 1 r/min-10 r/min, more preferably 3 r/min-4 r/min.
In the present invention, the high melt strength polybutene beads are prepared preferably in the length range of 1mm to 1.5mm and in the diameter range of 0.5mm to 1.5mm, more preferably 1.2 mm.
The preparation method provided by the invention is simple in process, easy in condition control and suitable for large-scale industrial production.
The invention also provides an application of the resin particle material in preparing a foaming material, wherein the resin particle material is the high-melt-strength polybutylene bead in the technical scheme.
In the present invention, the preparation method of the foaming material is preferably specifically:
injecting resin beads, a dispersing agent and water into an autoclave under the stirring condition and a physical foaming agent, heating to 100-160 ℃, boosting to 2-8 MPa, and keeping the pressure for 20-100 min after reaching the set temperature and pressure; after the pressure maintaining is finished, quickly opening a valve to release the pressure, spraying the beads into a cold water (5-25 ℃) cooling system, and quickly cooling to obtain a foaming material;
more preferably:
injecting resin beads, a dispersing agent and water into an autoclave under the stirring condition and a physical foaming agent, heating to 110-130 ℃, boosting to 4-6 MPa, and keeping the pressure for 50-70 min after reaching the set temperature and pressure; after the pressure maintaining is finished, the valve is opened quickly to release the pressure, and the beads are sprayed into a cold water (10-20 ℃) cooling system to be cooled quickly, so that the foaming material is obtained.
In the present invention, the resin beads are the high melt strength polybutene beads according to the above technical solution, and are not described herein again.
In the present invention, the dispersant is preferably linear alkyl benzene sulfonic acid sodium, calcium stearate, nano calcium carbonate, magnesium sulfate or calcium sulfate, more preferably linear alkyl benzene sulfonic acid sodium and nano calcium carbonate; the physical blowing agent is preferably carbon dioxide and/or nitrogen, more preferably carbon dioxide. The sources of the dispersant and the physical blowing agent in the present invention are not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the mass ratio of the resin beads, the dispersant and the water is preferably 1: (0.01-0.2): (3 to 100), more preferably 1: (0.01-0.1): (4-20).
The high melt strength particle containing the poly-1-butene prepared by the invention is a material suitable for foaming, and the foamed polybutylene further prepared by the invention is a compression-resistant buffering heat-insulating material, has excellent high-strength retraction resistance, shock absorption and energy absorption properties, low temperature resistance, chemical corrosion resistance, good environmental friendliness, is suitable for various forming modes, has the advantages of low cost, short period, controllable density and the like, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.
The invention provides high melt strength polybutylene beads and a preparation method and application thereof; the high melt strength polybutylene bead is prepared from the following raw materials: 100 parts by weight of a base resin; 0.1 to 1 weight part of antioxidant; the base resin is selected from one or more of poly-1-butene, poly-1-butene alloy, poly-1-butene random copolymer, graft-modified high melt strength material containing poly-1-butene; the melt flow index of the base resin is 0.1g/10 min-2 g/10 min. Compared with the prior art, the high melt strength polybutylene bead provided by the invention adopts specific content components, so that the integral better interaction is realized, the obtained high melt strength polybutylene bead has wider molecular weight distribution and excellent mechanical property, and is suitable for foaming; the further prepared foaming material has excellent high-strength anti-retraction property, shock absorption and energy absorption property, low temperature resistance, chemical corrosion resistance and good environment friendliness, is suitable for various foaming forming modes, has the advantages of low cost, short period, controllable density and the like, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.
In addition, the preparation method provided by the invention is simple in process, easy in condition control and suitable for large-scale industrial production.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available; wherein the melt flow index (190 ℃, 2.16Kg) of the poly-1-butene resin is 0.5g/10 min; the 1-butene copolymer resin (propane-butene copolymer) contains 90% of 1-butene, 10% of alpha-olefin (propylene) and 0.7g/10min of melt flow index (190 ℃, 2.16 Kg); the graft modified resin containing poly-1-butylene contains 95% of 1-butylene, 3% of alpha-olefin, 2% of grafting monomer and 2g/10min of melt flow index (190 ℃ and 2.16 Kg).
Example 1
(1) Drying the poly-1-butylene resin in a plastic mixing dryer for later use; placing the nucleating agent and the processing aid in a vacuum drying oven at 60 ℃ for drying for 12h for later use;
(2) weighing various dried raw materials according to a proportion, wherein the weight of the raw materials relative to the poly-1-butene resin is calculated by 100 parts of poly-1-butene resin, 0.2 part of nucleating agent nano silicon dioxide, 10100.075 parts of antioxidant, 1680.075 parts of antioxidant, 2 parts of cardanol, 0.2 part of PETA, 0.5 part of styrene, 0.05 part of calcium stearate and 0.2 part of initiator BIPB, placing the weighed raw materials in a high-speed mixer, stirring for 5min, and uniformly mixing the materials;
(3) adding the mixed materials into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged in a heating zone from a feed opening to a machine head, the temperature is set to 165 ℃, 180 ℃, 195 ℃, 200 ℃, the screw rotating speed is set to 130r/min, the feeding rotating speed is 3r/min, and after extrusion bracing, cooling, air cooling dehydration and grain cutting, small particles of the graft modified resin containing the poly-1-butene with the length of 1.5mm and the diameter of 1.2mm are obtained; i.e., high melt strength polybutene beads.
Example 2
(1) Drying the 1-butene copolymer resin (propane-butene copolymer) in a plastic mixing dryer for later use; placing the nucleating agent and the processing aid in a vacuum drying oven at 60 ℃ for drying for 12h for later use;
(2) weighing various dried raw materials according to a proportion, wherein the raw materials comprise 100 parts of 1-butene copolymer resin, 0.2 part of nucleating agent nano silicon dioxide, 10100.075 parts of antioxidant, 1680.075 parts of antioxidant, 2 parts of 1-octene, 0.2 part of PETA, 0.5 part of styrene, 0.05 part of calcium stearate and 1010.18 parts of initiator by weight relative to the 1-butene copolymer resin, placing the weighed raw materials in a high-speed mixer, stirring for 5min, and uniformly mixing the materials;
(3) adding the mixed materials into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, the feeding speed is 3r/min, the feeding speed is set to be 165 ℃, 180 ℃, 195 ℃, 220 ℃, 210 ℃, 130r/min, and the material is extruded, pulled into strips, cooled, air-cooled, dewatered and cut into granules to obtain 1.5mm long and 1.2mm diameter small particles of the graft modified resin containing the poly-1-butene; i.e., high melt strength polybutene beads.
Example 3
(1) Drying 1-butene copolymer resin (propane-butene copolymerization) and graft modified resin containing poly-1-butene in a plastic mixing dryer for later use;
(2) weighing various dried raw materials according to a proportion, wherein the weight of the raw materials relative to 1-butene copolymer resin is calculated as 100 parts of 1-butene resin copolymer, 150 parts of poly-1-butene graft modified resin, 10100.38 parts of antioxidant and 1680.38 parts of antioxidant, placing the weighed raw materials in a high-speed mixer, stirring for 5min, and uniformly mixing the materials;
(3) adding the mixed materials into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, the temperature is set to 165 ℃, 180 ℃, 190 ℃, the screw rotating speed is set to 260r/min, the feeding rotating speed is 4r/min, and the mixed materials are subjected to extrusion bracing, cooling, air cooling dehydration and grain cutting to obtain partially crosslinked modified resin small particles with the length of 1.5mm and the diameter of 1.2 mm; i.e., high melt strength polybutene beads.
Example 4
(1) Drying 1-butene copolymer resin (propane-butene copolymerization) and graft modified resin containing poly-1-butene in a plastic mixing dryer for later use;
(2) weighing various dried raw materials according to a proportion, wherein 100 parts of 1-butene resin copolymer, 67 parts of poly-1-butene graft modified resin, 10100.25 parts of antioxidant and 1680.25 parts of antioxidant are calculated by weight relative to 1-butene copolymer resin, putting the weighed raw materials into a high-speed mixer, stirring for 5min, and uniformly mixing the materials;
(3) adding the mixed materials into a parallel co-rotating twin-screw extruder, wherein 12 sections are arranged from a feed opening to a heating zone of a machine head, the temperature is set to 165 ℃, 180 ℃, 190 ℃, the screw rotating speed is set to 260r/min, the feeding rotating speed is 4r/min, and the mixed materials are subjected to extrusion bracing, cooling, air cooling dehydration and grain cutting to obtain partially crosslinked modified resin small particles with the length of 1.5mm and the diameter of 1.2 mm; i.e., high melt strength polybutene beads.
Application examples
The high melt strength polybutylene bead provided by the embodiment 1-4 of the invention is used for preparing the foaming material respectively, and the specific steps are as follows:
mixing the components in a mass ratio of 1: 0.01: 0.04: 5, injecting carbon dioxide into a high-pressure kettle under the stirring condition of the resin beads, the linear alkyl benzene sodium sulfonate, the nano calcium carbonate and the water, heating to 115 ℃, boosting to 5MPa, and keeping the pressure for 60min after reaching the set temperature and pressure; after the pressure maintaining is finished, the valve is opened rapidly to release the pressure, and the beads are sprayed into a cooling system with cold water (the temperature is 15 ℃) and cooled rapidly to obtain the foaming material.
The particle products obtained by the preparation methods provided by the embodiments 1-4 of the present invention and the foamed materials prepared therefrom are tested for various properties, and the results are shown in table 1.
TABLE 1 data of various properties of the granular products obtained by the preparation method provided in the embodiments 1-4 of the present invention and the foamed materials prepared therefrom
Figure BDA0003175116050000111
Figure BDA0003175116050000121
Note: the environment friendliness is that supercritical carbon dioxide is adopted for foaming in the foaming process, no toxic and harmful gas is generated, and compared with an EPS product, the EPS is easy to degrade and recover under certain conditions; the shrinkage rate is determined by testing the initial density immediately after foaming and the final density after constant temperature and humidity for 48 hours to obtain the difference value of the later multiplying power and the former multiplying power and dividing the difference value by the initial multiplying power to obtain the shrinkage rate; meanwhile, the foaming raw material polybutene has excellent chemical corrosion resistance, and the further prepared foaming material has excellent corrosion resistance.
As can be seen from Table 1, the high melt strength polybutylene bead provided by the invention is a closed cell foamed bead with uniform and compact cells and adjustable cell diameter, has high molecular weight, wide molecular weight distribution and excellent mechanical property, and is suitable for foaming; the further prepared foam material is a compression-resistant buffering heat-insulating material, has excellent high-strength retraction resistance, shock absorption and energy absorption, low temperature resistance, chemical corrosion resistance and good environmental friendliness, is suitable for various foaming forming modes, has the advantages of low cost, short period, controllable density and the like, and can be applied to the fields of military affairs, automobiles, buildings, toys, packaging materials and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The high melt strength polybutylene bead is prepared from the following raw materials:
100 parts by weight of a base resin;
0.1 to 1 weight part of antioxidant;
the base resin is selected from one or more of poly-1-butene, poly-1-butene alloy, poly-1-butene random copolymer, graft-modified high melt strength material containing poly-1-butene; the melt flow index of the base resin is 0.1g/10 min-2 g/10 min.
2. The high melt strength polybutene bead as claimed in claim 1, wherein the antioxidant is selected from one or more of hindered phenolic antioxidants, phosphite antioxidants and thioester antioxidants.
3. The high melt strength polybutene bead according to claim 1, wherein the high melt strength polybutene bead further comprises:
0.1 to 5 parts by weight of nucleating agent;
0.1 to 50 parts by weight of a graft monomer;
0.01-20 parts by weight of processing aid;
0.1 to 1 weight portion of initiator.
4. High melt strength polybutene beads according to claim 3, wherein the nucleating agent is selected from one or more of nano silica, talc, carbon black and nano calcium carbonate.
5. High melt strength polybutene beads as claimed in claim 3, wherein the grafting monomers are selected from one or more of cardanol, PETA, styrene and 1-octene.
6. High melt strength polybutene beads according to claim 3 wherein the processing aid is selected from one or more of calcium stearate, magnesium stearate and zinc stearate.
7. High melt strength polybutene beads as claimed in claim 3, wherein the initiator is selected from one or more of benzoyl peroxide, dicumyl peroxide, 2, 3-dimethyl-2, 3-diphenylbutane, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane and di-tert-butylperoxycumene.
8. A method for preparing high melt strength polybutene beads according to any one of claims 1 to 7, comprising the steps of:
a) the raw materials are uniformly mixed according to the component amount, added into a double-screw extruder to be extruded and pulled into strips, and then sequentially cooled, air-cooled to remove water and cut into granules, so that the high-melt-strength polybutene beads are obtained.
9. The preparation method of claim 8, wherein the twin-screw extruder in step a) has 12 sections from the feed opening to the heating zone of the head, and the sections are sequentially set to 160-170 ℃, 175-185 ℃, 190-195 ℃, 190-220 ℃, 190-210 ℃, the screw rotation speed is 100-300 r/min, and the feed rotation speed is 1-10 r/min.
10. Use of a resin particulate material in the preparation of a foamed material, wherein the resin particulate material is the high melt strength polybutene bead according to any one of claims 1 to 7.
CN202110829976.XA 2021-07-22 2021-07-22 High-melt-strength polybutylene bead as well as preparation method and application thereof Pending CN113563670A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110183713A (en) * 2019-06-25 2019-08-30 中国科学院青岛生物能源与过程研究所 A kind of preparation method of polybutene expanded bead (EPB)
CN110437380A (en) * 2019-07-10 2019-11-12 青岛青迈高能电子辐照有限公司 A kind of method of irradiation grafting preparation high-performance polybutene expanded bead (EPB)
CN110627959A (en) * 2019-06-25 2019-12-31 中国科学院青岛生物能源与过程研究所 Preparation method of high-strength high-toughness microporous polybutylene foam beads (EPB)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110183713A (en) * 2019-06-25 2019-08-30 中国科学院青岛生物能源与过程研究所 A kind of preparation method of polybutene expanded bead (EPB)
CN110627959A (en) * 2019-06-25 2019-12-31 中国科学院青岛生物能源与过程研究所 Preparation method of high-strength high-toughness microporous polybutylene foam beads (EPB)
CN110437380A (en) * 2019-07-10 2019-11-12 青岛青迈高能电子辐照有限公司 A kind of method of irradiation grafting preparation high-performance polybutene expanded bead (EPB)

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Application publication date: 20211029