CN101003587A - Method for preparing thermoplastic resin of stereoregularity by using segmented polymerizing body of liquid phase - Google Patents
Method for preparing thermoplastic resin of stereoregularity by using segmented polymerizing body of liquid phase Download PDFInfo
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Abstract
This invention discloses a method for preparing isotactic 1-butylene homopolymer or copolymers with other alpha-olefins by multi-stage liquid-phase bulk polymerization. The method comprises: adding metal catalyst into a reactor with stirrer, pre-polymerizing at a temperature below the polymerization temperature, and polymerizing 1-butylene or 1-butylene and other alpha-olefins at 30-70 deg.C and a certain pressure. The melt flow rate of the obtained polymer is 0.01-50 g/10 min (190 deg.C and 2.16 kg), and the isotacticity is higher than 92%. The molded product of the polymer has excellent heat resistance, low-temperature performance, processability, and high-temperature creep behavior, and can be used as resin for producing molded pipes. The method has such advantages as simple process, high efficiency and low cost, and the obtained polymer has such advantages as wide molecular weight distribution and good processability.
Description
Technical field
The invention belongs to field of polymer technology, relate to a kind of method that adopts liquid phase body stage feeding polymerization to prepare the stereospecific thermoplastic resin, relate in particular to a kind of high stereospecific 1-butylene homopolymer and with the novel synthesis of the multipolymer of other alpha-olefin, in particular, the synthetic method of high stereospecific polybutylene polymer involved in the present invention adopts liquid phase bulk depositing stage feeding polymerization, has the advantages that technical process is simple, efficient is high, cost is low.
Background technology
Usually, the poly-1-butylene resin of high isotactic is the hemicrystalline polylefin thermoplatic plastics of producing by isotactic Ziegler-Natta polyreaction, comprises homopolymer and a series of multipolymer.Have the polyethylene of being similar to and polyacrylic physical property, degree of crystallinity is between 50%～60%, fusing point is about 130 ℃, density is higher than polypropylene and is lower than polyethylene, the poly-general acid-and base-resisting of 1-butylene resin resin, solvent, paraffin oil and naphthenic oil, washing composition and various pharmaceutical chemicals, have outstanding resisting around property, anti-creep, resisting environmental stress and cracking, chemical-resistant resistance and wear-resistant, especially the high temperature creep resistant is the most outstanding, in that be no more than can be at 110 ℃ of life-time service under the stress of yield-point.The use temperature of poly-1-butylene resin resin can be used to make heat-pesistant thin film, hot water pipe, high strength hot melt adhesive etc. between-20～110 ℃, especially have excellent comprehensive performances aspect hot water pipe.
At present, the preparation method of the poly-1-butylene resin of high isotactic comprises solution method and vapor phase process, and wherein solution method comprises that again other hydro carbons is as solvent or self is as two kinds of methods of solvent.Other hydro carbons needs follow-up lock out operation as the liquid phase method of solvent, and the technology more complicated is polluted also bigger; The vapor phase process process is simple, but because 1-butylene polymkeric substance and 1-butylene monomer, other varsol have stronger affinity, polymkeric substance is easy to condense upon in the pipeline, and the security of operation, continuity are suffered damage, and adopts the regularity of the polymkeric substance that this method obtains not high.Adopting 1-butylene self is present more common polymerization process as solvent.
European patent EP 187034A2 report, adopt other alkene to carry out the homopolymerization of 1-butylene as solvent, at Ziegler-Natta catalyst, organo-aluminium compound, external electron donor, carry out polymerization under 20～45 ℃ of the polymerization temperatures, this technology need not to separate the non-rule content that has, but unreacted 1-butylene monomer and solvent mix, and catalytic efficiency is not high yet.
CN 87105646A report adopts the poly-1-butylene of the high isotactic of gas phase polymerization prepared, need not aftertreatment, and can simplify drying step greatly, but polymkeric substance is attached on reactor wall easily, and reaction efficiency is not high yet.
CN 1590417A reported and adopted the solution polymerization of carrying out 1-butylene under the protection of inert gas, obtained the lower high isotactic polymer of ash content, did not mention the bulk depositing point-score, and the molecular weight distribution of resulting polymers narrower (molecular weight distributing index is 3～6).
CN 1256698A report adopts special catalyzer (through the supported titanium catalyst of pure modification), TIBA, DIPMS, and by pre-polymerization, the polyreaction under two stage different conditions makes the poly-1-butylene of molecular weight distributing index about 6 then.The polymerization technique that adopts is liquid phase body and two kinds of methods of vapor phase process, and the shortcoming of this polymerization process is the Primary Catalysts that needs special raising molecular weight distribution, and reaction process is also complicated.
From present method, synthetic high normal poly-1-butylene resin is not that complex process is exactly harsh to the catalyzer requirement, and this just makes synthetic cost than higher, follows the PPR of similar purposes to compare, and poly-1-butylene resin does not have price advantage.Technical requirement simultaneously is also than higher.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts liquid phase body stage feeding polymerization to prepare the stereospecific thermoplastic resin, especially provide a kind of prepare stereospecific 1-butylene homopolymer or with the synthetic method of the multipolymer of other alpha-olefin.
Described novel synthesis is a liquid phase bulk depositing stage feeding polymerization, and it is simple to have technology, need not aftertreatment, and the products obtained therefrom particle diameter is even, and the energy consumption material consumption is low, and industrial scale is changeable.
The invention provides a kind of method that adopts liquid phase body stage feeding polymerization to prepare the stereospecific thermoplastic resin; be included in and add metal catalyst, promotor and external electron donor in the polymerization stirred autoclave; under protection of inert gas, carry out prepolymerization; and then make 1-butylene or 1-butylene and other alpha-olefin under 30～70 ℃, 0.001～0.9MPa pressure, carry out polyreaction, pass through H
2Regulate relative molecular mass.
Preferably, described polymerization process adopts liquid phase body (being bulk depositing) method, and product is the particle diameter homogeneous granules, need not aftertreatment and solvent is deviate from operation.
Preferably, described polymerization process is a stage feeding polymerization, and wherein the prepolymerization reaction temperature is at-10～20 ℃, and the pre-polymerization time was at 20～120 minutes; Be warmed up to 30～70 ℃ then, polymerization 1～12 hour.
Preferably, the isotactic content warp of described high stereospecific polymkeric substance
13C-NMR is determined as 92%～99%.(please provide scope)
Preferably, described alpha-olefin is selected from a kind of in ethene, propylene, 1-hexene, the 1-octene, and alpha-olefin alpha-olefin molar content is 0.01～10% of a 1-butylene.
Preferably, described metal catalyst is selected from MgCl
2The titanous chloride of load is catalyst based, titanium tetrachloride is catalyst based or SiO
2The titanous chloride of load is catalyst based, titanium tetrachloride is catalyst based, the metallocenes catalyzer; Promotor is selected from aluminum compound, the muriate of aluminum dialkyl, trialkylaluminium; External electron donor is selected from 1,4-Terpane, 1,8-Terpane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, o-benzene butyl phthalate ester etc.
Preferably, metal catalyst is MgCl
2Load titanium tetrachloride or metallocenes catalyzer; Aluminum compound comprises trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium; The muriate of aluminum dialkyl comprises the monochloride of diethyl aluminum, the monochloride of dioctyl aluminium; Trialkylaluminium is triethyl aluminum or triisobutyl aluminium; External electron donor is 1,8-Terpane or dimethoxydiphenylsilane.
Preferably, described rare gas element is a nitrogen.
Described novel synthesis is less demanding to catalyzer, and described loaded catalyst is selected from that the titanous chloride of MgCl2 carrying is catalyst based, titanium tetrachloride is catalyst based or SiO
2The titanous chloride of carrying is catalyst based, titanium tetrachloride is catalyst based, also can be independent catalyzer simultaneously, as metallocenes and thing catalyzer, and preferred MgCl
2Load titanium tetrachloride and metallocenes and thing catalyzer, more preferably MgCl
2The load titanium tetrachloride.Promotor is selected from aluminum compound, comprises trialkylaluminium, for example trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium etc.; The muriate of aluminum dialkyl is as the monochloride of diethyl aluminum, the monochloride of dioctyl aluminium etc.Wherein be preferably trialkylaluminium, best is triethyl aluminum and triisobutyl aluminium.External electron donor is selected from 1,4-Terpane, 1, and 8-Terpane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane, o-benzene butyl phthalate ester etc., wherein preferred 1,8-Terpane and dimethoxydiphenylsilane are regulated degree of isotacticity.Catalyzer easy, cost is low, the polymkeric substance of gained need not the deliming operation.
Described novel synthesis adopts the novel method of liquid phase bulk depositing stage feeding polymerization.Elder generation is under-20～30 ℃ of temperature under agitation condition, preferably-10～20 ℃, prepolymerization 10～120min, preferred 20～40min, be warmed up to 40～75 ℃ preferred 40～60 ℃ then and carry out polyreaction, regulate relative molecular mass by hydrogen, reacted 2～6 hours, transformation efficiency surpasses 40%, it is difficult that heat transfer becomes, power of agitator improves, termination reaction, and monomer can reuse through reclaiming; Also can adopt two still polymeric method reactors to comprise prepolymerization kettle and reflection still, in prepolymerization kettle, add catalyzer and a certain amount of 1-butylene monomer earlier, under above-mentioned reaction conditions pre-polymerization and, transfer to polymerization in the reactor then, and additional 1-butylene monomer, regulate relative molecular mass by hydrogen.Reaction terminating after vacuum-drying obtain the high degree of isotacticity of the uniform powder of particle diameter poly--the butylene resin.Better owing to gathering 1-butylene resin and 1-butylene monomer affinity in this technology, therefore control reaction temperature prevents that the polymkeric substance cohesion from being to react the key of carrying out smoothly, while stirring rake and stir speed (S.S.) require also strictness to prevent the stirring dead band and stirring is insufficient, thereby the polymkeric substance reunion occurs.The poly-1-butylene resin isotactic structural content warp that obtains by this technology polymerization
13C-NMR is determined as greater than 92%, molecular weight distribution (Mw/Mn) is higher than 6, and melt flow rate (MFR) is 0.01～50, preferred melt flow rate (MFR) 0.1～1.0, the polymkeric substance of gained has good thermotolerance, high temperature creep and high-speed molding, is the excellent materials of preparation cold and hot water.
For preventing that polymkeric substance from can add oxidation inhibitor at the high temperature ageing of devolatilization operation before the devolatilization operation, the oxidation inhibitor of being addressed comprises four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, the sulfo-diethylene is two, and [3-(3,5-di-t-butyl-4 hydroxy phenyl) propionic ester], β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide), tricresyl phosphite (2, the 4-di-tert-butyl-phenyl), 4,4 '-thiobis (the 6-tertiary butyl-3-cresols), 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, tetramethylolmethane four (3-lauryl thiopropionate), 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, β, β '-thio-2 acid SUNSOFT Q-182S etc. can be used two kinds and two or more common use also can making up wherein separately.
The poly-1-butylene resin that this method makes can also add UV light absorber, dyestuff, nucleator, lubricant, static inhibitor, filler and other resin etc. except that adding above-mentioned oxidation inhibitor.
The bright described novel synthesis of this law has the following advantages and innovates:
(1) technology is simple, and operation is few, is convenient to operation;
(2) less investment adopts bulk depositing stage feeding polymerization technology, with synthetic polymarization method for prodcing polyacrylates and equipment class seemingly, can significantly reduce contributed capital reconstructing on the synthetic polyacrylic equipment of body at present;
(3) the high isotactic poly-1-butylene resin of synthetic has wider molecular weight distribution, and processing characteristics is good, need not to add processing aid or adopts the method for the poly-1-butylene resin of the high melt speed of mechanical blending to improve processing characteristics, thereby destroy material physical property;
(4) other solvent is not used in environmental protection, the recyclable utilization of unreacted monomer;
(5) the high isotactic poly-1-butylene resin product of synthetic is little, the homogeneous granules of particle diameter, convenient processing.
Embodiment
Below enumerate the embodiment of the invention and comparative example and further specify the present invention, do not violating under the purport of the present invention, the present invention should be not limited to the content that following experimental example is specifically expressed.
Embodiment 1
The 1L polymeric kettle vacuumized and with nitrogen replacement for several times after, add a certain amount of 1-butylene monomer, triethyl aluminum, TiCl
4/ MgCl
2, dimethoxydiphenylsilane, prepolymerization is 30 minutes under-5 ℃ of conditions, temperature is raised to 50 ℃ of polyase 13s hour then in 30 minutes, and feeds H
2Regulate its relative molecular mass, hydrogen pressure is at 0.1MPa, and stir speed (S.S.) maintains 60 rev/mins, uses the ethanol termination reaction then.
The poly-1-butylene resin that obtains is done following performance test, and the results are shown in Table 1,
Embodiment 2
Adopt the 50ml flask to carry out prepolymerization, flask is vacuumized and with nitrogen replacement for several times after, add a certain amount of 1-butylene monomer, triethyl aluminum, TiCl
4/ MgCl
2, dimethoxydiphenylsilane, prepolymerization is 30 minutes under-5 ℃ of conditions, transfers to then in the 1L reactor that fills the 1-butylene monomer solution, reactor maintains the temperature at 50 ℃, stir speed (S.S.) is 60 rev/mins, reacts termination in 3 hours.
The poly-1-butylene resin that obtains is done following performance test, and the results are shown in Table 1,
Embodiment 3
The 1L polymeric kettle vacuumized and with nitrogen replacement for several times after, add a certain amount of 1-butylene monomer/vinyl monomer (mol ratio is 95/5), triethyl aluminum, TiCl
4/ MgCl
2, dimethoxydiphenylsilane, prepolymerization is 30 minutes under-5 ℃ of conditions, temperature is raised to 50 ℃ of polyase 13s hour then in 30 minutes, and feeds H
2Regulate its relative molecular mass, hydrogen pressure is at 0.1MPa, and stir speed (S.S.) maintains 60 rev/mins, uses the ethanol termination reaction then.
The poly-1-butylene resin that obtains is done following performance test, and the results are shown in Table 1,
Embodiment 4
The 1L polymeric kettle vacuumized and with nitrogen replacement for several times after, add a certain amount of 1-butylene monomer, triisobutyl aluminium, TiCl
4/ MgCl
2, 1, the 8-Terpane, prepolymerization is 45 minutes under 0 ℃ of condition, temperature is raised to 45 ℃ of polyase 13s hour then in 30 minutes, and feeds H
2Regulate its relative molecular mass, hydrogen pressure is at 0.1MPa, and stir speed (S.S.) maintains 60 rev/mins, uses the ethanol termination reaction then.
The poly-1-butylene resin that obtains is done following performance test, and the results are shown in Table 1, and the PB0110 properties of sample of this result and Basel is made comparisons.ASTM D2581 is pressed in specimen preparation.
Melt flow rate (MFR): press ASTM D1238,190 ℃ of probe temperatures, load 2.16Kg;
Isotactic index (mmmm%): adopt
13C-NMR tests.In tetracol phenixin, at 120 ℃, test frequency is at 50MHz with polymer dissolution, general wide 8KHz, and 6 pulse per second (PPS) repetition times are under 3600 conditions of scanning, by measuring this sample
13C-NMR composes and characterizes isotactic content;
Tensile strength, tensile yield: press the test of ASTM D638 plastic tensile experimental technique, draw speed 100mm/min;
Modulus in flexure: press ASTM D795 test;
Izod shock strength: press ASTM D256 plastics simply supported beam testing method;
Vicat softening point: press ASTM D648;
Density: adopt the test of hair method;
Shao Shi D type hardness tester: press ASTM D280 test;
Degree of crystallinity, fusing point, molten limit: adopt the DSC-204 test of the anti-company of speeding, N
2Under the protection, 10 ℃/min of heat-up rate;
Creep resistance: at 110 ℃, the 4Mpa pulling force, the velocity of variation of 1000 minutes elongations of test characterizes;
Mw/Mn: adopt Waters 150-C ALC/GPC to measure, earlier polymkeric substance is dissolved in 1 for 145 ℃, in the 2-dichlorobenzene, carry out the GPC test after filtering.Adopt known polystyrene standard as reference substance.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | PB0110 | |
| Melt flow rate (MFR)/g/10min | 0.49 | 0.40 | 0.2 | 0.35 | 0.47 |
| Isotactic index/% | 96.2 | 99.0 | 94.0 | 98.2 | 97.6 |
| Tensile strength/Mpa | 34.6 | 36.1 | 35.4 | 34.2 | 33.2 |
| Tensile yield/% | 380 | 360 | 390 | 354 | 340 |
| Around bent modulus/Mpa | 400 | 360 | 330 | 396 | 350 |
| Izod shock strength/KJ/m 3 | 42.6 | 47.8 | 46.2 | 44.7 | 46.5 |
| Creep resistance/% | 11.6 | 9.4 | 13.2 | 10.8 | 10.2 |
| Vicat softening point/℃ | 118.7 | 119.2 | 116.8 | 118.0 | 118.5 |
| Density/Kg/m 3 | 0.916 | 0.916 | 0.915 | 0.916 | 0.916 |
| Shao Shi D hardness/ | 60.5 | 60 | 59 | 60 | 60 |
| Mw/Mn | 6.9 | 6.0 | 6.8 | 6.0 | 6.3 |
| Degree of crystallinity/% | 55.2 | 50 | 48 | 51.9 | 54.8 |
| Fusing point/℃ | 125.8 | 126.2 | 124.0 | 126.0 | 125.6 |
| Molten limit/℃ | 10 | 10 | 10 | 10 | 10 |
Claims (8)
1, a kind of method that adopts liquid phase body stage feeding polymerization to prepare the stereospecific thermoplastic resin; be included in and add metal catalyst, promotor and external electron donor in the polymerization stirred autoclave; under protection of inert gas, carry out prepolymerization; and then make 1-butylene or 1-butylene and other alpha-olefin under 30～70 ℃, 0.001～0.9MPa pressure, carry out polyreaction, pass through H
2Regulate relative molecular mass.
2, a kind of employing liquid phase body stage feeding polymerization as claimed in claim 1 prepares the method for stereospecific thermoplastic resin, it is characterized in that, described polymerization process adopts liquid phase noumenal method, and product is the particle diameter homogeneous granules, need not aftertreatment and solvent is deviate from operation.
3, a kind of employing liquid phase body stage feeding polymerization as claimed in claim 1 prepares the method for stereospecific thermoplastic resin, it is characterized in that, described polymerization process is a stage feeding polymerization, and wherein the prepolymerization reaction temperature is at-10～20 ℃, and the pre-polymerization time was at 20～120 minutes; Be warmed up to 30～70 ℃ then, polymerization 1～12 hour.
4, a kind of employing liquid phase body stage feeding polymerization as claimed in claim 1 prepares the method for stereospecific thermoplastic resin, it is characterized in that the isotactic content warp of described high stereospecific polymkeric substance
13C-NMR is determined as 92%～99%.
5, a kind of employing liquid phase body stage feeding polymerization as claimed in claim 1 prepares the method for stereospecific thermoplastic resin, it is characterized in that, described alpha-olefin is selected from a kind of in ethene, propylene, 1-hexene, the 1-octene, and the alpha-olefin molar content is 0.01～10% of a 1-butylene.
6, a kind of employing liquid phase body stage feeding polymerization as claimed in claim 1 prepares the method for stereospecific thermoplastic resin, it is characterized in that described metal catalyst is selected from MgCl
2Catalyst based, the MgCl of the titanous chloride of load
2Catalyst based, the SiO of the titanium tetrachloride of load
2Catalyst based, the SiO of the titanous chloride of load
2Catalyst based or the metallocenes catalyzer of the titanium tetrachloride of load; Promotor is selected from aluminum compound, the muriate of aluminum dialkyl, trialkylaluminium; External electron donor is selected from 1,4-Terpane, 1,8-Terpane, dimethoxydiphenylsilane, diisopropyl dimethoxy silane or o-benzene butyl phthalate ester.
7, a kind of employing liquid phase body stage feeding polymerization as claimed in claim 6 prepares the method for stereospecific thermoplastic resin, it is characterized in that metal catalyst is MgCl
2Load titanium tetrachloride or metallocenes catalyzer; Aluminum compound comprises trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium; The muriate of aluminum dialkyl comprises the monochloride of diethyl aluminum, the monochloride of dioctyl aluminium; External electron donor is 1,8-Terpane or dimethoxydiphenylsilane.
8, a kind of employing liquid phase body stage feeding polymerization as claimed in claim 1 prepares the method for stereospecific thermoplastic resin, it is characterized in that described rare gas element is a nitrogen.
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| CN101550210B (en) * | 2009-03-10 | 2011-04-20 | 中国石化扬子石油化工有限公司 | High-density polyethylene resin and preparation method thereof |
| CN102050906A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Metallocene catalyst prepolymer and olefin polymerizing method thereof |
| CN103772557A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method for high isotactic polybutene-1 |
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| CN106432559A (en) * | 2015-08-04 | 2017-02-22 | 山东省滕州瑞达化工有限公司 | Liquid phase synthesis method of high isotactic polybutene-1 |
| CN110894249A (en) * | 2018-09-12 | 2020-03-20 | 中国石油化工股份有限公司 | Homogeneous polymerization method and device for butene-1 |
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| CN101550210B (en) * | 2009-03-10 | 2011-04-20 | 中国石化扬子石油化工有限公司 | High-density polyethylene resin and preparation method thereof |
| CN102050906A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Metallocene catalyst prepolymer and olefin polymerizing method thereof |
| CN103772557A (en) * | 2012-10-26 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method for high isotactic polybutene-1 |
| CN103772557B (en) * | 2012-10-26 | 2016-08-17 | 中国石油化工股份有限公司 | The preparation method of high isotactic PB Polybutene-1 |
| CN106432559A (en) * | 2015-08-04 | 2017-02-22 | 山东省滕州瑞达化工有限公司 | Liquid phase synthesis method of high isotactic polybutene-1 |
| CN106432559B (en) * | 2015-08-04 | 2020-11-17 | 山东省滕州瑞达化工有限公司 | High isotactic polybutene-1 liquid phase synthesis process |
| CN106084098A (en) * | 2016-07-29 | 2016-11-09 | 山东省滕州瑞达化工有限公司 | A kind of butylene 1 polymerization reaction kettle and butylene 1 polyreaction heat taking method |
| CN106084098B (en) * | 2016-07-29 | 2021-07-13 | 山东省滕州瑞达化工有限公司 | Butene-1 polymerization reaction kettle and butene-1 polymerization reaction heat taking method |
| CN110894249A (en) * | 2018-09-12 | 2020-03-20 | 中国石油化工股份有限公司 | Homogeneous polymerization method and device for butene-1 |
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