CN102304248B - Expandable high-melt-strength polypropylene resin and preparation method thereof - Google Patents
Expandable high-melt-strength polypropylene resin and preparation method thereof Download PDFInfo
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- CN102304248B CN102304248B CN2011102532574A CN201110253257A CN102304248B CN 102304248 B CN102304248 B CN 102304248B CN 2011102532574 A CN2011102532574 A CN 2011102532574A CN 201110253257 A CN201110253257 A CN 201110253257A CN 102304248 B CN102304248 B CN 102304248B
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- acrylic resin
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- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention discloses an expandable high-melt-strength polypropylene resin and a preparation method thereof. The method comprises: reacting and extruding raw materials including polypropylene, ultrahigh molecular weight polyethylene, petroleum resin, hyperoxide, bis[gamma-(triethoxysilyl)propyl]tetrasulfide, zinc oxide, stearic acid and the like in a parallel double screw extruder to obtain high-melt-strength polypropylene; and mixing the high-melt-strength polypropylene with liquid paraffin and azodicarbonamide at a high speed to obtain the expandable high-melt-strength polypropylene resin. The method disclosed by the invention is simple, low in investment and environment-friendly, and the extrusion performance of the melt is high.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of expandability high bath strength acrylic resin and preparation method thereof that has.
Background technology
Polypropylene is as a kind of thermoplasticity synthetic resins, have synthetic easily, characteristics such as little, nontoxic, the good heat resistance of density, rigidity height and electrical insulating property excellence, in industries such as automobile, household electrical appliances, packing and building materials, be widely used.But because polypropylene is as a kind of crystal polymer thing, when processing temperature is near its fusing point, its melt strength descends rapidly, thereby cause the hang down shortcoming of poor performance of the low and refractory of its melt strength, cause its container wall thickness when thermoforming inhomogeneous, during extrusion coated calendering edge curl, contraction appear, abscess problem such as subside during extrusion foaming.Therefore, polypropylene is subjected to very big restriction in the application in fields such as thermoforming, extrusion coated, blowing and foaming.
Polyacrylic foaming process essence is a drawing process of melt polypropylene, and bubble is grown up when foaming, also has to stretch when being subjected to stretching for the plain polypropylene melt to become the alkene characteristic, therefore can't be shaped to the polypropylene expanded body with high foamability.Given this, exploitation has the expandability high bath strength acrylic resin and has just become the important topic of pendulum in face of the scientific worker.
Abroad (Borealis, Korea S's Hunan chemical industry etc.) at present with the high fondant-strength industrialization, and in global marketing, obtains applications well in the high foaming of polypropylene field especially in thermoforming, extrusion coated, blowing.Domesticly recently also begin the research of high melt strength, propylene, obtained certain effect.But because existing treatment process adopts irradiation method mostly, though the feasible equipment of this method has high input, industrialization at present is few.Research is more in the chemical graft process, but a large amount of organic solvents of the employing that has or easy volatile monomer produce considerable influence to environment, disclose a kind of high bath strength acrylic resin and preparation method thereof as CN1775851A.This high bath strength acrylic resin is by comprising that weight percent is that 30 ~ 80% graft polypropylene, 10 ~ 50% polypropylene, 2 ~ 10% metallocene PE resin, 2 ~ 10% aminated compounds and other auxiliary agent of surplus are formed.Preparation method of the present invention is for after mixing the graft polypropylene resin of formula ratio and homopolymerization, copolymerization PP raw material, metallocene PE resin, various auxiliary agent in the high-speed mixing still, joining temperature from spout is that 180 ~ 220 ℃, L/D are 36: 1 ~ 48: 1 the twin screw extruder, add the aminated compounds acetone soln in screw rod the 4th district by precision metering pump, vacuumize granulation and form.
In sum, exploitation have less investment, environmental protection to have an expandability high bath strength acrylic resin imperative.
Summary of the invention
In view of the deficiencies in the prior art, the object of the present invention is to provide a kind of expandability high bath strength acrylic resin and preparation method thereof that has, this polyacrylic melt strength height, this preparation method when improving the melt strength of acrylic resin, production process environmental protection, feasible.
In order to realize purpose of the present invention, the contriver has obtained following technical scheme by a large amount of experimental studies:
A kind of have an expandability high bath strength acrylic resin, is prepared from by polypropylene, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide, two-[γ-(triethoxysilicane) propyl group] tetrasulfide and other auxiliary agent.
In the embodiment of a preparation high bath strength acrylic resin of the present invention, described other auxiliary agents are antioxidant 1010s.Preferably, this high bath strength acrylic resin is prepared from by each component by following weight part:
| Polypropylene | 100 parts |
| Petroleum resin | 1-10 part |
| Ultrahigh molecular weight polyethylene(UHMWPE) | 1-5 part |
| Dicumyl peroxide | 0.1-2 part |
| Two-[γ-(triethoxysilicane) propyl group] tetrasulfide | 0.6-2 part |
| Antioxidant 1010 | 0.1-0.5 part. |
In the embodiment of another preparation expandability high bath strength acrylic resin of the present invention, described other auxiliary agents are mixtures of antioxidant 1010, zinc oxide, stearic acid, azo two formyl ammonia and whiteruss.Preferably, this expandability high bath strength acrylic resin is prepared from by each component by following weight part:
| Polypropylene | 100 parts |
| Petroleum resin | 1-10 part |
| Ultrahigh molecular weight polyethylene(UHMWPE) | 1-5 part |
| Dicumyl peroxide | 0.1-2 part |
| Two-[γ-(triethoxysilicane) propyl group] tetrasulfide | 0.6-2 part |
| Antioxidant 1010 | 0.1-0.5 part |
| Zinc oxide | 1-5 part |
| Stearic acid | 1-5 part |
| Azo two formyl ammonia | 0.1-20 part |
| Whiteruss; | 0.1-0.3 part. |
The method that provides two kinds to prepare high bath strength acrylic resin is provided second purpose of the present invention:
Method one: the preparation method of high bath strength acrylic resin, comprise polypropylene, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide and two-[γ-(triethoxysilicane) propyl group] tetrasulfide, antioxidant 1010 in mixing machine with 900-1200 rev/min, 60 ℃ were stirred 15 minutes down, the back adds in the forcing machine of two rank: this pair rank forcing machine wherein single order is parallel double-screw extruder, the forcing machine length-to-diameter ratio is 40:1, screw diameter 75 mm, 100-400 rev/min of parallel double-screw extruder rotating speed, the temperature of twin screw extruder from the transportation section to the discharge port is 190-210 ℃; Second rank are single screw extrusion machine, the forcing machine length-to-diameter ratio is 15:1, and screw diameter 150, single screw extrusion machine are rotating speed 25-50 rev/min, forcing machine is 150-190 ℃ from the transportation section to the temperature of mouth mould and reacts extruding pelletization, obtains a kind of high bath strength acrylic resin.
Method two: the preparation method with expandability high bath strength acrylic resin, comprise polypropylene, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide, two-[γ-(triethoxysilicane) propyl group] tetrasulfide, antioxidant 1010 and zinc oxide, stearic acid in mixing machine with 900-1200 rev/min, 60 ℃ were stirred 15 minutes down, the back adds in the forcing machine of two rank: this pair rank forcing machine wherein single order is parallel double-screw extruder, the forcing machine length-to-diameter ratio is 40:1, screw diameter 75mm, 100-400 rev/min of parallel double-screw extruder rotating speed, the temperature of twin screw extruder from the transportation section to the discharge port is 190-210 ℃; Second rank are single screw extrusion machine, the forcing machine length-to-diameter ratio is 15:1, and screw diameter 150, single screw extrusion machine are rotating speed 25-50 rev/min, forcing machine is 150-190 ℃ from the transportation section to the temperature of mouth mould and reacts extruding pelletization, obtains a kind of high bath strength acrylic resin D;
Acrylic resin D and azo two formyl ammonia and whiteruss were stirred 15 minutes down with 900-1200 rev/min, 60 ℃ in mixing machine, obtain a kind of high bath strength acrylic resin E with expandability, acrylic resin E is added in the single screw extrusion machine, rotating speed 20-30 rev/min, single screw extrusion machine is 160-210 ℃ from the transportation section to the temperature of mouth mould, extrusion foaming can obtain extruding the polypropylene expanded body of homogeneous.
Polypropylene of the present invention comprises the disclosed various types of acrylic resins of prior art, comprises homo-polypropylene resin, Co-polypropylene resin etc.
Ultrahigh molecular weight polyethylene(UHMWPE) of the present invention refers to that molecular-weight average is at the polyethylene of 250-350 ten thousand.The high melt strength, propylene that its existence can effectively prevent from inventing is in extrusion, and viscosity occurs than great fluctuation process.
Petroleum resin of the present invention refer to the copolymer resins of the alicyclic C 5 petroleum resin of dicyclopentadiene, C 5/C nine copolymerized petroleum resins, carbon five and other material.Petroleum resin are as crosslinking coagent, and its adding can promote the combination between the polypropylene macromole, form long branched chain structure.
Of the present invention pair-[γ-(triethoxysilicane) propyl group] tetrasulfide (Si-69), it mainly acts on is the effect of playing stabilized radical in the process of preparation branched p 0 lypropylene.In preparation process, the tertiary carbon macromolecular radical instability that polypropylene forms, at high temperature, do not have under the situation of Si-69 auxiliary agent, polyacrylic degraded plays a leading role, and causes degradation of polypropylene serious; And under the situation that the Si-69 auxiliary agent is arranged, can reduce the concentration of polypropylene macromolecular radical, and suppress polyacrylic degraded, be conducive to polypropylene branching or little crosslinked.
Whiteruss of the present invention is No. 5 white oils, and its adding is conducive to the polypropylene surface that obtained high fondant-strength is dispersed and sticked to whipping agent.
Compared with prior art, a kind of acrylic resin that the present invention relates to and preparation method thereof has following advantage and marked improvement: (1) melt polypropylene degree height, its melt strength are 5 times of plain polypropylene.(2) no volatile solvent in the course of processing.(3) the material foam performance is good, and foam density is less than 0.2 gram/cubic centimetre during extrusion foaming.
Embodiment
Further specify the present invention below by embodiment.The preparation method of the embodiment of the invention is only used for illustrating the present invention, rather than limitation of the present invention, and the simple modifications to preparation method of the present invention under design prerequisite of the present invention all belongs to the scope of protection of present invention.
The preparation of embodiment one high bath strength acrylic resin
Method one: will form polypropylene among the A, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide and two-[γ-(triethoxysilicane) propyl group] tetrasulfide, oxidation inhibitor by proportioning and in mixing machine, stir 15 minutes down with 900-1200 rev/min, 60 ℃, the back adds in the forcing machine of two rank: this pair rank forcing machine wherein single order is parallel double-screw extruder, the forcing machine length-to-diameter ratio is 40:1, screw diameter 75,100-400 rev/min of parallel double-screw extruder rotating speed, the temperature of twin screw extruder from the transportation section to the discharge port is 190-210 ℃.Second rank are single screw extrusion machine, the forcing machine length-to-diameter ratio is 15:1, and screw diameter 150, single screw extrusion machine are 25-50 rev/mins of rotating speeds, forcing machine is 150-190 ℃ from the transportation section to the temperature of mouth mould and reacts extruding pelletization, obtains a kind of high bath strength acrylic resin.
Method two: by proportioning will form A with form among the B raw material in mixing machine with 900-1200 rev/min, 60 ℃ stirrings 15 minutes down, the back adds in the forcing machine of two rank: this pair rank forcing machine wherein single order is parallel double-screw extruder, the forcing machine length-to-diameter ratio is 40:1, screw diameter 75,100-400 rev/min of parallel double-screw extruder rotating speed, the temperature of twin screw extruder from the transportation section to the discharge port is 190-210 ℃.Second rank are single screw extrusion machine, the forcing machine length-to-diameter ratio is 15:1, and screw diameter 150, single screw extrusion machine are 25-50 rev/mins of rotating speeds, forcing machine is 150-190 ℃ from the transportation section to the temperature of mouth mould and reacts extruding pelletization, obtains a kind of high bath strength acrylic resin D.
In proportion resin D and composition C were stirred 15 minutes down with 900-1200 rev/min, 60 ℃ in mixing machine again, obtain a kind of high bath strength acrylic resin E with expandability, E is added in the single screw extrusion machine, 30 rev/mins of rotating speeds, single screw extrusion machine is 160-210 ℃ from the transportation section to the temperature of mouth mould, extrusion foaming can obtain extruding the polypropylene expanded body of homogeneous.Compared with prior art have advantages such as no volatile solvent in melt polypropylene degree height, the course of processing, material foam performance are good according to the sample of this method preparation; Its melt strength is 5 times of plain polypropylene, and foam density is less than 0.2 gram/cubic centimetre during extrusion foaming.
The preparation of embodiment two high bath strength acrylic resins
Its preparation method is with embodiment one.
The preparation of embodiment three high bath strength acrylic resins
Change homo-polypropylene into homo-polypropylene and the polyacrylic mixture of copolymerization, homo-polypropylene accounts for 1-99% in the mixture, and making method is with embodiment one.
Claims (4)
1. one kind has the expandability high bath strength acrylic resin, it is characterized in that: be prepared from by polypropylene, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide, two-[γ-(triethoxysilicane) propyl group] tetrasulfide and other auxiliary agent; Described ultrahigh molecular weight polyethylene(UHMWPE) is that molecular-weight average is at the polyethylene of 250-350 ten thousand; Described petroleum resin are the copolymer resins of the alicyclic C 5 petroleum resin of dicyclopentadiene, carbon five and other material; Described other auxiliary agents are antioxidant 1010s;
Described have an expandability high bath strength acrylic resin, is prepared from by each component by following weight part:
100 parts of polypropylene
Petroleum resin 1-10 part
Ultrahigh molecular weight polyethylene(UHMWPE) 1-5 part
Dicumyl peroxide 0.1-2 part
Two-[γ-(triethoxysilicane) propyl group] tetrasulfide 0.6-2 part
Antioxidant 1010 0.1-0.5 part.
2. one kind has the expandability high bath strength acrylic resin, it is characterized in that: be prepared from by polypropylene, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide, two-[γ-(triethoxysilicane) propyl group] tetrasulfide and other auxiliary agent; Described ultrahigh molecular weight polyethylene(UHMWPE) is that molecular-weight average is at the polyethylene of 250-350 ten thousand; Described petroleum resin are the copolymer resins of the alicyclic C 5 petroleum resin of dicyclopentadiene, carbon five and other material; Described other auxiliary agents are mixtures of antioxidant 1010, zinc oxide, stearic acid, Cellmic C 121 and whiteruss;
Described have an expandability high bath strength acrylic resin, is prepared from by each component by following weight part:
100 parts of polypropylene
Petroleum resin 1-10 part
Ultrahigh molecular weight polyethylene(UHMWPE) 1-5 part
Dicumyl peroxide 0.1-2 part
Two-[γ-(triethoxysilicane) propyl group] tetrasulfide 0.6-2 part
Antioxidant 1010 0.1-0.5 part
Zinc oxide 1-5 part
Stearic acid 1-5 part
Cellmic C 121 0.1-20 part
Whiteruss 0.1-0.3 part.
3. the described preparation method with expandability high bath strength acrylic resin of claim 1, it is characterized in that: with polypropylene, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide and two-[γ-(triethoxysilicane) propyl group] tetrasulfide, antioxidant 1010 in mixing machine with 900-1200 rev/min, 60 ℃ were stirred 15 minutes down, the back adds in the forcing machine of two rank: this pair rank forcing machine wherein single order is parallel double-screw extruder, the forcing machine length-to-diameter ratio is 40:1, screw diameter 75 mm, 100-400 rev/min of parallel double-screw extruder rotating speed, the temperature of twin screw extruder from the transportation section to the discharge port is 190-210 ℃; Second rank are single screw extrusion machine, the forcing machine length-to-diameter ratio is 15:1, and screw diameter 150, single screw extrusion machine are rotating speed 25-50 rev/min, forcing machine is 150-190 ℃ from the transportation section to the temperature of mouth mould and reacts extruding pelletization, obtains a kind of high bath strength acrylic resin.
4. the described preparation method with expandability high bath strength acrylic resin of claim 2, it is characterized in that: with polypropylene, petroleum resin, ultrahigh molecular weight polyethylene(UHMWPE), dicumyl peroxide, two-[γ-(triethoxysilicane) propyl group] tetrasulfide, antioxidant 1010 and zinc oxide, stearic acid in mixing machine with 900-1200 rev/min, 60 ℃ were stirred 15 minutes down, the back adds in the forcing machine of two rank: this pair rank forcing machine wherein single order is parallel double-screw extruder, the forcing machine length-to-diameter ratio is 40:1, screw diameter 75mm, 100-400 rev/min of parallel double-screw extruder rotating speed, the temperature of twin screw extruder from the transportation section to the discharge port is 190-210 ℃; Second rank are single screw extrusion machine, the forcing machine length-to-diameter ratio is 15:1, and screw diameter 150, single screw extrusion machine are rotating speed 25-50 rev/min, forcing machine is 150-190 ℃ from the transportation section to the temperature of mouth mould and reacts extruding pelletization, obtains a kind of high bath strength acrylic resin D;
Acrylic resin D and Cellmic C 121 and whiteruss were stirred 15 minutes down with 900-1200 rev/min, 60 ℃ in mixing machine, obtain a kind of high bath strength acrylic resin E with expandability, acrylic resin E is added in the single screw extrusion machine, rotating speed 20-30 rev/min, single screw extrusion machine is 160-210 ℃ from the transportation section to the temperature of mouth mould, extrusion foaming can obtain extruding the polypropylene expanded body of homogeneous.
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| CN103923382B (en) * | 2014-03-14 | 2016-04-06 | 湖北工业大学 | A kind of low melting point height can cementability expanded polypropylene beads and preparation method thereof |
| CN104610506A (en) * | 2015-01-04 | 2015-05-13 | 南通日之升高分子新材料科技有限公司 | High-melt strength polypropylene and preparation method thereof |
| CN106279965A (en) * | 2015-06-11 | 2017-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of physical blowing fills anti-flaming polypropylene material and preparation method thereof |
| CN106750992B (en) * | 2016-12-15 | 2019-03-01 | 广东圆融新材料有限公司 | A kind of low gloss, low-odor polypropylene ene compositions and preparation method thereof |
| CN107163477A (en) * | 2017-05-26 | 2017-09-15 | 合肥会通新材料有限公司 | One kind can directly be molded chemical micro-foaming polypropylene composite material and preparation method thereof |
| CN109777064B (en) * | 2017-11-14 | 2021-07-23 | 万华化学集团股份有限公司 | Extrusion-grade polycarbonate alloy material and preparation method and application thereof |
| CN109762229B (en) * | 2018-12-24 | 2021-11-30 | 浙江万里新材料科技有限公司 | Irradiation crosslinking polyethylene foam material and preparation method thereof |
| CN109824955B (en) * | 2018-12-24 | 2021-07-06 | 浙江万里新材料科技有限公司 | Irradiation crosslinking polyethylene foam material and preparation method thereof |
| CN111117073A (en) * | 2020-01-09 | 2020-05-08 | 山东清河化工科技有限公司 | Blending type ultrahigh molecular weight polypropylene/polypropylene alloy and preparation method thereof |
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| CN1037776C (en) * | 1995-10-05 | 1998-03-18 | 中国石化茂名石油化工公司 | Polypropylene toughness-increasing modified material and preparing method |
| DE19727981A1 (en) * | 1997-07-01 | 1999-01-07 | Buna Sow Leuna Olefinverb Gmbh | Molding compound based on ultra high molecular weight polyethylene and process for its production |
| CN1207337C (en) * | 2003-05-13 | 2005-06-22 | 北京度辰新材料股份有限公司 | High-intercluding transparent polypropylene resin composition, sheet made of the composition and its making process |
| CN101735545B (en) * | 2009-12-29 | 2011-08-31 | 丹阳市华东工程塑料有限公司 | High rigidity light composite board for automobile roof and preparation method thereof |
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