CN107226877A - Increase firm acrylic resin and preparation method thereof - Google Patents
Increase firm acrylic resin and preparation method thereof Download PDFInfo
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- CN107226877A CN107226877A CN201710472575.7A CN201710472575A CN107226877A CN 107226877 A CN107226877 A CN 107226877A CN 201710472575 A CN201710472575 A CN 201710472575A CN 107226877 A CN107226877 A CN 107226877A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Increase firm acrylic resin and preparation method thereof the invention provides one kind.This method comprises the following steps：By ethene, propylene under the catalytic action of ziegler natta catalyst, it is polymerize by gas phase hydrogen-regulating method, and reinforcement nucleating agent is added in the granulation for powders stage, so as to prepares the firm acrylic resin of increasing；Wherein, the internal electron donor of ziegler natta catalyst is two ethers internal electron donors.In this method, the internal electron donor of ziegler natta catalyst is two ethers internal electron donors, such internal electron donor can strengthen the catalytic activity and stereoselectivity of catalyst, it can also improve the isotacticity of polymer simultaneously, making the xylene soluble content of acrylic resin reduces, and this is conducive to the rigidity for improving acrylic resin.Meanwhile, reinforcement nucleating agent is added during the extruding pelletization in later stage, also being capable of crystal grain thinning, the crystal property of raising resin, so as to improve its rigidity.
Description
Technical field
The present invention relates to polypropylene material preparing technical field, in particular to the firm acrylic resin of increasing and its preparation
Method.
Background technology
In recent years, developed rapidly and polypropylene product with auto industry, bullet train, construction industry, electronics communications industry
High performance, polyacrylic yield and demand are greatly improved, as fastest-rising general-purpose plastics nearly ten years.
At present, usually using ethylene-propylene copolymer manufacture low flowing impact resistance resin, although above-mentioned resin it is firm
Property and toughness substantially meet downstream user demand, but the widening using field with automobile application and plastic blend, to above-mentioned
The rigidity and impact resistance of resin propose higher demand.
For these reasons, it is necessary to provide it is a kind of increase firm acrylic resin, it is had higher rigidity and shock resistance concurrently
Property.
The content of the invention
The present invention is intended to provide a kind of increase firm acrylic resin and preparation method thereof, to solve to produce eutectic in the prior art
Body propylene impact hits the technical problem that polypropylene rigidity can be undesirable.
To achieve these goals, according to an aspect of the invention, there is provided a kind of preparation for increasing firm acrylic resin
Method, it comprises the following steps：By ethene, propylene under the catalytic action of Ziegler-Natta catalyst, pass through gas phase hydrogen-regulating method
It is polymerize, and reinforcement nucleating agent is added in the granulation for powders stage, so as to prepares the firm acrylic resin of increasing；Wherein, Ziegler-receive
The internal electron donor of tower catalyst is two ethers internal electron donors.
Further, preparation method comprises the following steps：By Ziegler-Natta catalyst, co-catalyst, outer electron
Body, hydrogen and propylene mix and carry out the first polymerisation, obtain containing first polymer in head product, head product；By primiparity
Thing, hydrogen, ethene and propylene are mixed, and hydrogen, ethene and propylene is carried out the second polymerisation, are obtained second polymer,
And then obtain the secondary product containing head product and second polymer；Secondary product is carried out after catalyst inactivation and drying process, added
Plus reinforcement nucleating agent and extruding pelletization, obtain increasing firm acrylic resin.
Further, the melt flow rate (MFR) of head product is 4~5g/10min；The melt flow rate (MFR) of secondary product is 1.5
~2.5g/10min.
Further, in secondary product, the percetage by weight of ethene is 9~10%.
Further, the weight ratio of first polymer and second polymer is 7:3~9:1.
Further, co-catalyst is alkane machine aluminium compound；Preferably, alkyl aluminum is trialkyl aluminium compound；More preferably
Ground, trialkyl aluminium compound is selected from by triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum and tri-n-octylaluminium
One or more in the group of composition；It is further preferred that alkyl aluminum is triethyl aluminum.
Further, external electron donor is alkoxy silane compound；Preferably, alkoxy silane compound is two
Cyclopenta dialkoxy silicane；It is highly preferred that bicyclopentyl dialkoxy silicane is dicyclopentyl dimethoxyl silane and/or two
Cyclopenta diethoxy silane.
Further, with the molar ratio computing of Al elements and Si elements, the amount ratio of co-catalyst and external electron donor for 1~
6。
Further, reinforcement nucleating agent is selected from by inorganic reinforcement nucleating agent, aryl phosphoric acids salt reinforcement nucleating agent, class mountain
Pears alcohols reinforcement nucleating agent, phosphate metal salt reinforcement nucleating agent, class rosin reinforcement nucleating agent, dehydroabietic acid and its esters increase
One or more in the group of firm nucleator and carboxylic acid metal's salt reinforcement nucleating agent composition.
Further, reinforcement nucleating agent be aryl phosphoric acids salt reinforcement nucleating agent, more preferably aryl phosphoric acids salt increase just into
Core agent is NA11 or NA21.
Further, the addition of reinforcement nucleating agent is 500~1000ppm.
Further, the temperature of the first polymerisation is 60~70 DEG C, and pressure is 2.0~2.5MPa；Second polymerisation
Temperature be 60~70 DEG C, pressure be 2.0~2.5MPa.
Further, Ziegler-Natta catalyst also includes titanium compound and carrier, and titanium compound at least contains one
Titanium-halogen key；Preferably, carrier is dialkoxy magnesium.
According to another aspect of the present invention, a kind of firm acrylic resin of increasing is additionally provided, it is prepared by above-mentioned preparation method
Form.
Apply the technical scheme of the present invention, ethene, propylene are passed through into gas phase hydrogen under the catalysis of Ziegler-Natta catalyst
Tune method prepares acrylic resin.The internal electron donor of Ziegler-Natta catalyst is two ethers internal electron donors, such interior to electricity
Daughter can strengthen the catalytic activity and stereoselectivity of catalyst, while can also improve the isotacticity of polymer, make poly- third
The xylene soluble content reduction of olefine resin, this is conducive to the rigidity for improving acrylic resin.Meanwhile, made in the extrusion in later stage
Reinforcement nucleating agent is added during grain, also being capable of crystal grain thinning, the crystal property of raising resin, so as to improve its rigidity.More than
Both sides factor so that the firm acrylic resin of increasing that the present invention is provided has excellent rigidity and shock resistance concurrently, is a kind of
The strong and unyielding acrylic resin having both.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.The present invention is described in detail below in conjunction with embodiment.
In the prior art, although the strong and unyielding performance of acrylic resin meets downstream user demand, but with automobile application
With plastic blend widening using field, its rigidity increasingly can not meet the growing demand of user with impact resistance.
For above-mentioned technical problem, according to the present invention, a kind of typical embodiment there is provided a kind of preparation for increasing firm acrylic resin
Method.The preparation method comprises the following steps：By ethene, propylene under the catalytic action of Ziegler-Natta catalyst, pass through gas
Phase hydrogen-regulating method is polymerize, and adds reinforcement nucleating agent in the granulation for powders stage, so as to prepare the firm acrylic resin of increasing；Wherein,
The internal electron donor of Ziegler-Natta catalyst is two ethers internal electron donors.
In the above-mentioned preparation method that the present invention is provided, ethene, propylene are passed through under the catalysis of Ziegler-Natta catalyst
Gas phase hydrogen-regulating method prepares acrylic resin.The internal electron donor of Ziegler-Natta catalyst is two ethers internal electron donors, is used
Two ethers internal electron donors can strengthen the catalytic activity and stereoselectivity of catalyst, at the same can also improve polymer etc.
Normality, making the xylene soluble content of acrylic resin reduces, and this is conducive to the rigidity for improving acrylic resin.Meanwhile,
Reinforcement nucleating agent is added during the extruding pelletization in later stage, also being capable of crystal grain thinning, the crystal property of raising resin, so as to improve
Its rigidity.Factor of both the above so that the firm acrylic resin of increasing that the present invention is provided has excellent rigidity and shock resistance concurrently
Performance, is a kind of strong and unyielding acrylic resin having both.
Added by using the Ziegler-Natta catalyst with two ethers internal electron donors, and in the extruding pelletization stage
Reinforcement nucleating agent, you can be effectively improved the rigidity of acrylic resin, make it have rigidity and shock resistance concurrently.A kind of preferred
In embodiment, at least to be produced by the Innovene gas phase polypropylene polymerization techniques two-stage polymerization of Ineos companies, i.e., it is above-mentioned
Preparation method comprises the following steps：Ziegler-Natta catalyst, co-catalyst, external electron donor, hydrogen and propylene are mixed simultaneously
The first polymerisation is carried out, obtains containing first polymer in head product, head product；And by head product, hydrogen, ethene and third
Alkene is mixed, and hydrogen, ethene and propylene is carried out the second polymerisation, obtains second polymer, and then obtain time product；Will
Secondary product is carried out after catalyst inactivation and drying process, addition reinforcement nucleating agent and extruding pelletization, obtains increasing firm acrylic resin.
Low melt stream successively can be prepared in the first gas-phase polymerization using gas-phase polymerization twice in above-mentioned polymerization technique
The first polymer (i.e. Noblen) of dynamic speed, is then added to the second polymerization anti-by the head product containing first polymer
Ying Zhong, in head product in the presence of the material with catalytic activity, hydrogen, propylene, ethene carry out the second polymerisation, obtain
The second polymer existed in propylene-ethylene rubber phase form, and then obtain the secondary product containing head product and second polymer.
The second polymer existed in the form of propylene-ethylene rubber phase has higher rigidity and impact resistance, thus when propylene is poly-
When having first polymer and second polymer simultaneously in compound, the shock resistance and rigidity of the acrylic polymers are able into one
Step lifting.
In a preferred embodiment, the melt flow rate (MFR) of head product is 4~5g/10min；The melt of secondary product
Flow rate is 1.5~2.5g/10min.Can more effectively it be controlled according to the data of the melt flow rate (MFR) of monitoring final poly-
The property of allyl resin.And, polypropylene tree. successively control by melt flow rate (MFR) of head product and time product within the above range
The rigidity and shock resistance of fat are more preferably；The xylene soluble content in first polymer is less than 1.5wt% simultaneously, can make
Obtain acrylic polymers rigidity and toughness keeps balance.In the preparation process in accordance with the present invention, those skilled in the art can be by adjusting
The density of hydrogen for saving the polymerization system of the first and second polymer controls the polymerization of the first polymerisation and the second polymerisation
The melt flow rate (MFR) of thing.
In above-mentioned preparation method, due to the difference in terms of reaction temperature, pressure, external electron donor and internal electron donor,
So that the reactivity of the second polymerisation is different, and then make it that the content of ethene in acrylic polymers is different.
It is a kind of preferred embodiment in, in above-mentioned product the percetage by weight of ethene be 9~10%.By ethylene unit in polymer
In weight than control be conducive within the above range further improve acrylic polymers impact resistance and rigid balancing.
, can be by the way that oxygen and/or nitrogen gas concn will be passed through in the second polymerisation in the preparation method that the present invention is provided
Ratio of the percentage by volume control propylene-ethylene rubber in acrylic resin.In a preferred embodiment,
The weight ratio of one polymer and second polymer is 7:3~9:1, preferably 8:2~9:1.First polymer is polymerize with second
The mixing ratio control of thing within the above range, can further improve the overall mechanical properties of acrylic resin.
In the preparation method that the present invention is provided, those skilled in the art can select conventional organo-aluminum compound conduct
Co-catalyst.In a preferred embodiment, co-catalyst is alkane machine aluminium compound；Preferably, alkyl aluminum is trialkyl
Aluminium compound；It is highly preferred that trialkyl aluminium compound is selected from by triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, three n-hexyls
One or more in the group of aluminium and tri-n-octylaluminium composition.Above-mentioned co-catalyst can be adsorbed on a catalyst support, be formed
Activated centre, this is conducive to the catalytic activity for further improving catalyst, makes xylene soluble content in acrylic resin
It is lower, so that its rigidity is more.It is further preferred that alkyl aluminum is triethyl aluminum (TEAL).
In the preparation process in accordance with the present invention, the external electron donor of selection can be any external electron donor.It is excellent in one kind
In the embodiment of choosing, external electron donor includes but is not limited to alkoxy silane compound.Can be after using such electron donor
The continuous ratio for improving ziegler-natta catalyst systems high isotactic activated centre, can make to polymerize the polymer isotacticity come
Higher, the random thing of generation is less, and research shows：The silane of this structure is best raising Ziegler-Natta catalyst body
It is a kind of silane of isotacticity.Preferably, alkoxy silane compound is bicyclopentyl dialkoxy silicane；It is highly preferred that
Bicyclopentyl dialkoxy silicane is dicyclopentyl dimethoxyl silane and/or bicyclopentyl diethoxy silane.
In the preparation process in accordance with the present invention, those skilled in the art can select the co-catalyst and external electron donor added
Amount ratio.In a preferred embodiment, with Al elements and the molar ratio computing of Si elements, co-catalyst and outer electron
The amount ratio of body is 1~6.The addition of external electron donor is adjusted, the stereoselectivity of catalyst can be correspondingly adjusted.Will be outer
The consumption control of electron donor within the above range, also can further improve the catalytic activity and control stereotaxis of catalyst
Property, so as to effectively control polymer performance, and further improve the rigidity of acrylic resin.
According to a kind of typical embodiment of the present invention, reinforcement nucleating agent is selected from by inorganic reinforcement nucleating agent, aryl phosphorus
Barbiturates reinforcement nucleating agent, class glucitols reinforcement nucleating agent, phosphate metal salt reinforcement nucleating agent, class rosin increase firm nucleation
One or more in the group of agent, dehydroabietic acid and its esters reinforcement nucleating agent and carboxylic acid metal's salt reinforcement nucleating agent composition.
It is preferred that, inorganic reinforcement nucleating agent be talcum powder, calcium oxide, carbon black, calcium carbonate, mica, inorganic pigment or kaolin, preferably
Talcum powder or mica, addition 500-1000ppm；Aryl phosphoric acids salt reinforcement nucleating agent is NA11, NA21, addition 500-
1000ppm；Glucitols reinforcement nucleating agent is DBS, MDBS, DMDBS or 3988, NX8000.
It is highly preferred that reinforcement nucleating agent is aryl phosphoric acids salt reinforcement nucleating agent, most preferably N A11 or NA21.And phase
Compared with N A11, using NA21 as reinforcement nucleating agent, can further crystal grain thinning, improve crystalling propylene performance, so as to enter one
Step makes acrylic resin have high rigidity and high impact resistance concurrently.It is further preferred that the addition of reinforcement nucleating agent be 500~
1000ppm。
In the preparation method that the present invention is provided, those skilled in the art can select the technique of gas-phase polymerization processes twice
Parameter.In a preferred embodiment, the temperature of the first polymerisation is 60~70 DEG C, and pressure is 2.0~2.5MPa；The
The temperature of dimerization reaction is 60~70 DEG C, and pressure is 2.0~2.5MPa.
In a preferred embodiment, catalyst also includes at least containing in titanium compound and carrier, and titanium compound
There is a titanium-halogen key.Preferably, carrier is dialkoxy magnesium.According to the above-mentioned teaching of the present invention, those skilled in the art can be with
The consumption of electron and titanium compound in selecting catalyst.In a preferred embodiment, interior electron in catalyst
The weight percentage of body is 5~15%, and the weight percentage of titanium compound is 1~3%.Catalyst mineral in the present invention
Oil is diluted to 30wt% concentration.
In a word, above-mentioned ziegler-natta catalyst systems include the solids containing titanium composition as active component, and it includes titanium
Electron in compound, magnesium compound, halogen, the inorganic oxide as carrier and two ethers as electron donor compound
Body, and alkyl aluminum compound, organosilan external electron donor system.Ziegler-natta catalyst systems for the present invention
Comprising ingredient of solid catalyst, the component includes at least one titanium compound and at least one with least one titanium-halogen key
Internal electron donor, the two is preferably all carried on dialkyl magnesium carrier.
In addition, increasing firm acrylic resin present invention also offers one kind, it is prepared from by above-mentioned preparation method.The increasing
Firm acrylic resin has high rigidity and high shock resistance concurrently.
Beneficial effects of the present invention are further illustrated below in conjunction with embodiment：
Data are obtained in embodiments of the invention in accordance with the following methods, can be according to this area conventional meanses if not indicating
Obtain.
The melt flow rate (MFR) of polymer be according to ISO1133,230 DEG C/2.16kg obtain.
The assay method of ethene, according to applied chemistry the 5th phase in 2009《Fourier transform infrared spectrometry quickly determines second
Ethylene contents in propylene copolymer》Method is determined.
Bending modulus and impact strength are tested according to GBT 9341-2008 and GB-T1843-1996.
Polymerisation process explanation
It is interior to electricity containing the diether compound of alkyl 1,3 using forth generation ziegler-natta catalyst systems catalyst
Daughter system, the catalyst is diluted to 30wt% concentration with mineral oil.
First step gas-phase polymerization, catalyst, triethyl aluminum, external electron donor, hydrogen and charging propylene, in temperature 60~70
DEG C, under 2.0~2.5MPa pressure, the head product of manufacture enters second reactor.65 DEG C of preferable temperature, 2.3MPa is, it is necessary to control
Xylene soluble part is less than 1.5%, melt flow rate (MFR) 4-5g/10min.
Second step gas-phase polymerization, at 60~70 DEG C of temperature, 2.0~2.5MPa pressure, catalyst and propylene, ethene, hydrogen
Gas-phase (co-) polymerisation, polymer enters degassing unit, and 65 DEG C of preferable temperature, 2.3MPa controls rubber using the mixture of nitrogen and oxygen
Generation ratio.
Polymer obtains increasing firm acrylic resin, carries out related test again through inactivation and drying process, extruding pelletization.
Comparative example and embodiment data are shown in Table 1.
Table 1
Continued 1
As can be seen from the above description, the above embodiments of the present invention realize following technique effect：
Catalyst system changes and addition reinforcement nucleating agent can significantly improve the rigidity and rigid-tough balance of material.Make
With dicyclopentyl dimethoxyl silane and addition reinforcement nucleating agent, material stiffness can be significantly improved.Especially, use
NA11, NA21, especially NA21, can significantly improve material stiffness, and resin is had rigid-tough balance..
The low flowing anti-impact of the gas phase hydrogen-regulating method production of the present invention increases firm acrylic resin manufacture method, uses a kind of height
Stereotaxis internal electron donor and Innovene gas-phase polymerization process, also added reinforcement nucleating agent etc., the firm polypropylene tree of the increasing
Fat can be widely applied to injection molding art, but be not limited to the field.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (14)
1. a kind of preparation method for increasing firm acrylic resin, it is characterised in that comprise the following steps：By ethene, propylene in neat lattice
Under the catalytic action of Le-Natta catalyst, it is polymerize by gas phase hydrogen-regulating method, and addition increases firm nucleation in the granulation for powders stage
Agent, so as to prepare the firm acrylic resin of increasing；Wherein, the internal electron donor of the Ziegler-Natta catalyst is two ethers
Internal electron donor.
2. preparation method according to claim 1, it is characterised in that the preparation method comprises the following steps：
The Ziegler-Natta catalyst, co-catalyst, external electron donor, hydrogen and propylene are mixed and the first polymerization is carried out
Reaction, obtains containing first polymer in head product, the head product；
The head product, hydrogen, ethene and propylene are mixed, hydrogen, ethene and propylene is carried out the second polymerisation, obtains
To second polymer, and then obtain the secondary product containing the head product and the second polymer；
Described product is carried out after catalyst inactivation and drying process, the reinforcement nucleating agent and extruding pelletization is added, obtains
It is described to increase firm acrylic resin.
3. preparation method according to claim 2, it is characterised in that the melt flow rate (MFR) of the head product is 4~5g/
10min；The melt flow rate (MFR) of described product is 1.5~2.5g/10min.
4. preparation method according to claim 3, it is characterised in that in described product, the percetage by weight of ethene is 9
~10%.
5. the preparation method according to any one of claim 2 to 4, it is characterised in that the first polymer and described
The weight ratio of second polymer is 7:3~9:1.
6. the preparation method according to any one of claim 2 to 4, it is characterised in that the co-catalyst is alkane machine aluminium
Compound；Preferably, the alkyl aluminum is trialkyl aluminium compound；It is highly preferred that the trialkyl aluminium compound is selected from by three
One or more in the group that aluminium ethide, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum and tri-n-octylaluminium are constituted；Enter
Preferably, the alkyl aluminum is triethyl aluminum to one step.
7. preparation method according to claim 6, it is characterised in that the external electron donor is alkoxyl silicone alkanes chemical combination
Thing；Preferably, the alkoxy silane compound is bicyclopentyl dialkoxy silicane；It is highly preferred that the bicyclopentyl
Dialkoxy silicane is dicyclopentyl dimethoxyl silane and/or bicyclopentyl diethoxy silane.
8. preparation method according to claim 7, it is characterised in that described with Al elements and the molar ratio computing of Si elements
The amount ratio of co-catalyst and the external electron donor is 1~6.
9. preparation method according to any one of claim 1 to 4, it is characterised in that the reinforcement nucleating agent be selected from by
Inorganic reinforcement nucleating agent, aryl phosphoric acids salt reinforcement nucleating agent, class glucitols reinforcement nucleating agent, phosphate metal salt increase firm
Nucleator, class rosin reinforcement nucleating agent, dehydroabietic acid and its esters reinforcement nucleating agent and carboxylic acid metal's salt reinforcement nucleating agent
One or more in the group of composition.
10. preparation method according to claim 9, it is characterised in that the reinforcement nucleating agent is the aryl orthophosphate
Class reinforcement nucleating agent, more preferably described aryl phosphoric acids salt reinforcement nucleating agent is NA11 or NA21.
11. preparation method according to claim 10, it is characterised in that the addition of the reinforcement nucleating agent is 500~
1000ppm。
12. the preparation method according to any one of claim 2 to 4, it is characterised in that the temperature of first polymerisation
Spend for 60~70 DEG C, pressure is 2.0~2.5MPa；The temperature of second polymerisation be 60~70 DEG C, pressure be 2.0~
2.5MPa。
13. preparation method according to claim 1, it is characterised in that the Ziegler-Natta catalyst also includes titanizing
Compound and carrier, and the titanium compound is at least containing a titanium-halogen key；Preferably, the carrier is dialkoxy magnesium.
14. one kind increases firm acrylic resin, it is characterised in that as the preparation method system any one of claim 1 to 13
It is standby to form.
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| CN109501423A (en) * | 2018-11-26 | 2019-03-22 | 铜陵熙成塑料制品有限公司 | A kind of cement package bags membrane material |
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| CN109679010A (en) * | 2017-10-19 | 2019-04-26 | 中国石油天然气股份有限公司 | Preparation method of high impact polypropylene |
| CN109679010B (en) * | 2017-10-19 | 2022-02-01 | 中国石油天然气股份有限公司 | Preparation method of high impact polypropylene |
| CN108299735A (en) * | 2018-03-21 | 2018-07-20 | 山东京博石油化工有限公司 | A kind of method that interval small capital body technology prepares high just acrylic resin |
| CN109501423A (en) * | 2018-11-26 | 2019-03-22 | 铜陵熙成塑料制品有限公司 | A kind of cement package bags membrane material |
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Application publication date: 20171003 |