CN112300495A - Silicon dioxide and propane-butadiene copolymer compound and preparation method thereof - Google Patents
Silicon dioxide and propane-butadiene copolymer compound and preparation method thereof Download PDFInfo
- Publication number
- CN112300495A CN112300495A CN201910707185.2A CN201910707185A CN112300495A CN 112300495 A CN112300495 A CN 112300495A CN 201910707185 A CN201910707185 A CN 201910707185A CN 112300495 A CN112300495 A CN 112300495A
- Authority
- CN
- China
- Prior art keywords
- silicon dioxide
- propylene
- propane
- silica
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- C08F210/08—Butenes
Abstract
The invention relates to a compound of silicon dioxide and a propyl-butyl copolymer and a preparation method thereof, wherein the mass content of the propyl-butyl copolymer is 5-99%, and the mass content of the silicon dioxide is 1-95%. After the polymerization of propylene, 1-butene and functional olefin monomers is completed, silica slurry is added for repolymerization to form the composite of the invention. The molecular chain of the propane-butane copolymer is firmly combined with the surface of silicon dioxide in a chemical bond mode by polymerizing propylene, 1-butene and functional olefin monomers (containing Si-Cl bonds), introducing Si-Cl bonds into the molecular chain of the propane-butane copolymer, and carrying out chemical reaction on the Si-Cl bonds and a large number of silicon hydroxyl groups (Si-OH) existing on the surface of the silicon dioxide to generate Si-O-Si bonds. The preparation method has the characteristics of simple preparation process, uniform dispersion of silicon dioxide, high product strength, good toughness and stable performance.
Description
Technical Field
The invention relates to a synthetic resin material and a preparation method thereof, in particular to a compound of silicon dioxide and a propane-butadiene copolymer and a preparation method thereof.
Background
The polypropylene is a polyolefin resin material with huge yield, has excellent performance, easy processing and low cost, and has wide application in the production and living fields. Polypropylene has the disadvantages of poor low temperature toughness and high processing temperature, which limits its applications to some extent. The polypropylene can be modified by copolymerizing propylene with olefin monomers such as ethylene, 1-butene and the like, and the copolymerization can not only reduce the melting point of the polypropylene so as to reduce the hot processing temperature of the material, but also endow the material with more excellent impact resistance. For example, propylene copolymerized with a small amount of 1-butene (less than 10%) gives a propylene resin which is useful as a film material having a low heat seal initiation temperature, and which has good mechanical properties and a low melting point. The literature (Macromol. chem. Phys.2005,206,2333-2341) reports the preparation of propylene/1-butene copolymers in a gas-phase polymerization process using Ziegler-Natta catalysts, with a molar content of 1-butene of up to 15% (mass content 19%), the remainder being propylene. The toughness of the resin can be further improved by continuing to increase the 1-butene content, but the rigidity is seriously impaired. Chinese patent 201010198121.3 discloses a poly-1-butene alloy material, which mainly comprises a blend of homo-polymerization 1-butene (50% -99%), homo-polymerization polypropylene (1-40%) and propylene/1-butene copolymer (the content is less than 10%), wherein the rigidity of the material is kept by a homopolymer with a high proportion, and the toughness of the material is improved by a small amount of copolymer.
It is a demand for polypropylene to have high performance without impairing the rigidity of the material while improving the toughness of the material. A common approach is to add a reinforcing component, such as an inorganic filler, to the resin. The silicon dioxide is used as an important filler, and the addition of the silicon dioxide can not only improve the physical and mechanical properties of products and reduce the cost of the products, but also improve the processing performance of materials. However, the silica surface has a strong polarity due to a large amount of silicon hydroxyl (Si-OH), has a high surface energy, and is very likely to cause an agglomeration phenomenon. The silica which has not been surface-treated is generally difficult to disperse, and tends to exist in the form of aggregates in the resin matrix, failing to sufficiently exert the reinforcing effect. Furthermore, if the dispersion of the silicon dioxide can be realized in the synthesis process of the propane-butadiene copolymer, the propane-butadiene copolymer with stable dispersion of the silicon dioxide and excellent performance can be directly prepared in a polymerization kettle, and the method has important practical value and long-term environmental protection significance.
Disclosure of Invention
The invention aims to provide a compound of silicon dioxide and a propane-butadiene copolymer, wherein the composition of the propane-butadiene resin is as follows: the mass content of the propane-butadiene copolymer is 5-99%, and the mass content of the silicon dioxide is 1-95%; the propylene-butylene copolymer is a copolymer formed by polymerizing propylene, 1-butylene and a functional olefin monomer, wherein the molar content of propylene units in the copolymer is 5-95%, the molar content of 1-butylene units in the copolymer is 5-95%, and the molar content of functional olefin monomer units in the copolymer is 0.01-50%.
The invention provides a compound of silicon dioxide and a propane-butadiene copolymer, wherein the functional olefin monomer has the following structure:
wherein R is1And R2Which may be the same or different, is selected from the group consisting of Cl, methyl, ethyl, isopropyl, methoxy, ethoxy, isopropoxy; n is an integer of 1 to 12. The functional olefin monomer may be, but is not limited to: allyldimethylchlorosilane, allyltrichlorosilane, 3-butenyldimethylchlorosilane, 3-butenyltrichlorosilane, 5-hexenylmethyldichlorosilane, 5-hexenyltrichlorosilane, 7-octenyldimethylchlorosilane, (4-vinyl) phenyl-dimethylchlorosilane, (4-vinyl) phenyl-methyldichlorosilane, (4-vinyl) phenyltrichlorosilane, (4-vinyl) benzyl-dimethylchlorosilane, (4-vinyl) benzyl-methyldichlorosilane, (4-vinyl) benzyl-trichlorosilane, (4-vinyl) phenethyl-dimethylchlorosilane, (4-vinyl) phenethyl-dichlorosilaneMethyldichlorosilane, (4-vinyl) phenethyl-trichlorosilane, and the like.
The functional olefin monomer is a compound with double functional groups: the first functional group is an olefin double bond, and the function of the first functional group is to participate in the copolymerization of propylene and 1-butene to prepare propane-butene resin; the second functional group is a silicon-chlorine bond (containing 1-3), and has the function of chemically reacting with hydroxyl on the surface of the silicon dioxide to generate a Si-O-Si bond, so that chemical bonding is generated between the propyl-butyl copolymer and the silicon dioxide.
The compound of the silicon dioxide and the propane-butadiene copolymer provided by the invention is prepared by a direct in-kettle polymerization method, and mainly comprises the following steps:
(1) adding 1-butene, functional olefin monomer, propylene monomer and cocatalyst into a polymerization reactor, and finally adding a main catalyst to carry out polymerization reaction. Wherein the mass ratio of the added 1-butene to the propylene is 1-10000: 100, the ratio of the added functional olefin monomer to the sum of the mass of the added propylene and the mass of the added 1-butene is 0.01-5: 1, the polymerization temperature is 0-100 ℃, the polymerization pressure is 0.2-6 MPa, and the polymerization time is 0.1-6 hours; the main catalyst is selected from Ziegler-Natta catalyst or metallocene catalyst, and the cocatalyst is selected from alkyl aluminium compound or alkyl aluminoxane compound;
(2) and preparing silicon dioxide slurry. Adding an organic solvent and silicon dioxide powder into the batching tank, and stirring to form silicon dioxide slurry, wherein the mass ratio of the silicon dioxide to the organic solvent is 0.1-10: 1. the organic solvent is not particularly limited, and for example, n-pentane, n-hexane, n-heptane, petroleum ether, cyclohexane, or the like can be used.
(3) Adding the silicon dioxide slurry obtained in the step (2) into the polymerization product obtained in the polymerization reactor obtained in the step (1), controlling the stirring speed of the polymerization reactor to be 50-500 rpm, and controlling the mass ratio of the silicon dioxide to the polymer to be 0.02-19: 1, the mass of the silicon dioxide slurry added at the rate of one minute is 1-10% of the mass of the polymerization product in the step (1) in the reactor; after the addition is finished, reacting for 0.1-5 hours; and after the reaction is finished, removing the residual unreacted 1-butene and propylene monomers to obtain the compound of silicon dioxide and propane-butadiene resin.
Further, in the above technical solution, preferably, the ratio of the added functional olefin monomer to the sum of the mass of the added propylene and 1-butene is 0.1 to 3: 1; the polymerization reaction temperature is 30-80 ℃; the polymerization pressure is 0.2-4 MPa; the polymerization time is 0.5 to 3 hours.
Further, in the above-mentioned technical means, preferably, the Ziegler-Natta procatalyst is a transition metal catalyst supported on a magnesium halide; the transition metal is selected from Ti and V (titanium and vanadium); the content of the transition metal element is 0.1-10% (mass content); further preferably, the Ziegler-Natta procatalyst is MgCl2Supported TiCl4A catalyst; the Ziegler-Natta catalyst also contains an internal electron donor component, wherein the internal electron donor component is selected from diethyl succinate, dibutyl adipate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, 2-diisobutyl-1, 3-dimethoxypropane or 9, 9-bis (methoxymethyl) fluorene; the content of the internal electron donor is 0.1-20% (mass content).
Further, in the above-mentioned technical means, it is preferable that the metallocene catalyst is selected from transition metal-pi bond compounds having a transition metal of Ti, Zr or Hf as a central atom; further preferably, the transition metal-pi bond compound having a transition metal Ti, Zr or Hf as a central atom is selected from C2H4(Me4Cp)2MCl2，C2H4(Ind)2MCl2，C2H4(2,4,7-Me3-Ind)2MCl2，Me2Si(Flu)2MCl2，Me2SiCH2(Ind)2MCl2，Me2Si(2-MeInd)2MCl2，Me2Si(2,5-Me-Cp)2MCl2，Me2Si(4,7-Me2-Ind)2MCl2，Me2Si(2-Me-4-Naph-Ind)2ZrCl2(ii) a In the above compounds, Me ═ methyl, Ph ═ phenyl, Cp ═ cyclopentadienyl, Ind ═ indenyl, H4Ind ═ 4,5,6, 7-tetrahydroindene, Flu ═ fluorenyl, Naph ═ naphthyl, and M is selected from Ti, Zr, or Hf.
Further, in the above-mentioned technical solution, it is preferable that when the main catalyst employs a Ziegler-Natta catalyst, the co-catalyst is selected from an alkyl aluminum compound; when the main catalyst is metallocene catalyst, the cocatalyst is selected from alkyl aluminoxane compounds.
Further, in the above technical solution, preferably, the aluminum alkyl is a trialkyl aluminum or a mixture of trialkyl aluminum and alkyl aluminum halide or alkyl aluminum polyhalide, wherein the trialkyl aluminum is preferably at least one of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum, and the alkyl aluminum halide is preferably diethyl aluminum chloride; the polyhaloalkylaluminum is preferably triethylaluminum trichloride;
further, in the above technical solution, preferably, the alkylaluminoxane is preferably at least one of methylaluminoxane and isobutylaluminoxane.
The addition amount of the cocatalyst is calculated by the molar ratio of Al to Ti or V, Al in the Ziegler-Natta catalyst and M (M ═ Ti, Zr or Hf) in the metallocene catalyst, and respectively is Al: ti or V is 10 to 20000, preferably 50 to 1000; al: m is 10 to 20000, preferably 500 to 10000.
Further, in the above technical means, the silica is preferably a particulate silica having a particle diameter in the range of 0.05 to 50 μm, more preferably a particulate silica having a particle diameter in the range of 0.1 to 20 μm; preferably, the reaction time of the polymerization product and the silica is 0.5 to 3 hours.
According to the invention, by adopting a polymerization method of propylene, 1-butene and functional olefin monomers (containing Si-Cl bonds), Si-Cl bonds are introduced into the molecular chain of the propyl-butyl copolymer, and the Si-Cl bonds and a large amount of silicon hydroxyl (Si-OH) existing on the surface of silicon dioxide can perform chemical reaction to generate Si-O-Si bonds, so that the molecular chain of the propyl-butyl copolymer is firmly combined with the surface of the silicon dioxide in the form of the chemical bonds, and the problem of weak interaction between the propyl-butyl copolymer and the silicon dioxide is fundamentally solved; meanwhile, the silica particles are completely separated by the polymer due to the wrapping of the propyl-butyl copolymer on the silica particles, so that the problem of easy agglomeration of the silica is fundamentally solved. The compound of the silicon dioxide and the propane-butane copolymer provided by the invention has the characteristics of simple preparation process, uniform silicon dioxide dispersion, high strength, good toughness and stable performance, and can completely avoid the phenomenon of silicon dioxide agglomeration.
Drawings
FIG. 1 is a scanning electron micrograph of a quenched face of the composite of example 1, at 350 times magnification.
FIG. 2 is a scanning electron micrograph of the quenched face of the composite of example 1, at 6000 Xmagnification.
Detailed Description
Functional olefin monomer:
the olefin monomers containing Si-Cl bonds can be purchased from commercial sources or can be directly synthesized by any method in the prior art. For the synthesized Si-Cl bond-containing monomer, the present application provides a general synthesis method, and does not limit the Si-Cl bond-containing monomer. Functional olefin monomer a 1: allyldimethylchlorosilane, available from carbofuran chemical (CAS number: 4028-23-3). The structural formula is as follows:
functional olefin monomer a 2: allyl trichlorosilane, available from carbofuran chemistry (CAS number: 107-37-9). The structural formula is as follows:
functional olefin monomer B1:
under the protection of nitrogen, adding 24.3g of magnesium tape polished by sand paper into a three-neck round-bottom flask provided with a constant pressure dropping funnel and a reflux condenser, adding 100mL of dried Tetrahydrofuran (THF) and 9.7g of p-chlorostyrene into the constant pressure dropping funnel, dropwise adding the mixture into the three-neck round-bottom flask, and reacting for 2 hours to obtain dark gray suspension; the suspension was added dropwise to a round-bottomed flask containing 50mL of dried THF and 11.21g of dimethyldichlorosilane under nitrogen protection, and reacted at room temperature for 16 hours; finally, removing THF (tetrahydrofuran) under reduced pressure, adding dry n-hexane to dissolve out a product, and filtering to obtain a crude product; adding 0.3g of 4-methoxyphenol, and distilling at 110-120 ℃ under reduced pressure to obtain a functional olefin monomer B1 ((4-vinyl) phenyl-dimethylchlorosilane). The structural formula is as follows:
functional olefin monomer B2:
by adopting the synthetic route of the functional monomer B1, the functional olefin monomer B2, (4-vinyl) phenyl-trichlorosilane is obtained by replacing 14.8g of silicon tetrachloride with dimethyl silicon dichloride. The structural formula is as follows:
functional olefin monomer C:
under the protection of nitrogen, adding 24.3g of magnesium tape polished by sand paper into a three-neck round-bottom flask provided with a constant pressure dropping funnel and a reflux condenser, adding 100mL of dried Tetrahydrofuran (THF) and 10.9g of (4-vinyl) benzyl-chloromethane into the constant pressure dropping funnel, dropwise adding the mixture into the three-neck round-bottom flask, and reacting for 2 hours to obtain dark gray suspension; dropwise adding the suspension into a round-bottom flask containing 50mL of dried THF and 11.21g of silicon methyl trichloride under the protection of nitrogen, and reacting for 16 hours at room temperature; finally, removing THF (tetrahydrofuran) under reduced pressure, adding dry n-hexane to dissolve out a product, and filtering to obtain a crude product; adding 0.3g of 4-methoxyphenol, and distilling at 120-130 ℃ under reduced pressure to obtain a functional olefin monomer C ((4-vinyl) benzyl-methyldichlorosilane). The structural formula is as follows:
comparative experiment 1 (Synthesis of a propylene-butylene copolymer without addition of a functional olefin monomer and silica)
Into a 2L reactor, 250g of propylene and 250g of 1-butene were charged, and 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2The carrier is Ti of 2.3 wt%, dibutyl phthalate of 9.6 wt% as internal electron donor and diethyl phthalate of 1.7 wt%, and the copolymerization product of 310g is obtained after reaction for 0.5 hour at 70 ℃. The propylene content of the copolymer was 56.5 mol%, and the 1-butene content was 43.5 mol%. The composition and basic properties of the copolymers are shown in Table 1.
Comparative experiment 2 (Synthesis of a propylene-butylene copolymer with addition of functional olefin monomer, without addition of silica)
Into a 2L reactor, 250g of propylene and 250g of 1-butene were charged, 2.5mol of a functional olefin monomer A1 was added, 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2Is taken as a carrier, contains 2.3 weight percent of Ti, 9.6 weight percent of dibutyl phthalate as an internal electron donor and 1.7 weight percent of diethyl phthalate), and reacts for 0.5 hour at 70 ℃ to obtain 330g of copolymerization product. The copolymer had a propylene content of 52.7 mol%, a 1-butene content of 38.8 mol%, and a functional monomer A1 content of 8.5 mol%. The composition and basic properties of the copolymers are shown in Table 1.
Example 1
Into a 2L reactor, 250g of propylene and 250g of 1-butene were charged, 2.5mol of a functional olefin monomer A1 was added, 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2Is used as a carrier, contains 2.3 weight percent of Ti, 9.6 weight percent of dibutyl phthalate as an internal electron donor, and 1.7 weight percent of diethyl phthalate), and reacts for 0.5 hour at 70 ℃.
113g of silicon dioxide and 100g of hexane solution are added into a batching tank, the mixture is added into the polymerization reaction kettle by a screw pump after being uniformly stirred, the feeding speed of the screw pump is controlled to be 10g/min, and the reaction kettle is stirred and reacted for 2 hours at room temperature at the stirring speed of 100 rpm. The product was collected and dried to yield 443g of product.
The mass content of the propane-butadiene copolymer in the product is 74.5 wt%, and the mass content of the silicon dioxide is 25.5 wt%; in the propylene-butadiene copolymer, the propylene content was 52.7 mol%, the 1-butene content was 38.8 mol%, the functional monomer A1 content was 8.5 mol%, and the basic properties of the polymer are shown in Table 1.
Example 2
Into a 2L reactor, 250g of propylene and 250g of 1-butene were charged, 2.5mol of a functional olefin monomer A2 was added, 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2Is used as a carrier, contains 2.3 weight percent of Ti, 9.6 weight percent of dibutyl phthalate as an internal electron donor, and 1.7 weight percent of diethyl phthalate), and reacts for 0.5 hour at 70 ℃.
282g of silicon dioxide and 150g of hexane solution are added into a batching tank, the mixture is added into the polymerization reaction kettle by a screw pump after being stirred uniformly, the feeding speed of the screw pump is controlled to be 10g/min, and the reaction kettle is stirred and reacted for 2 hours at room temperature at the stirring speed of 100 rpm. The product was collected and dried to yield 612 g.
The mass content of the propane-butadiene copolymer in the product is 53.9 wt%, and the mass content of the silicon dioxide is 46.1 wt%; in the propylene-butadiene copolymer, the propylene content was 52.7 mol%, the 1-butene content was 38.8 mol%, the functional monomer A2 content was 8.5 mol%, and the basic properties of the polymer are shown in Table 1.
Example 3
Into a 2L reactor, 250g of propylene and 250g of 1-butene were charged, 2.5mol of a functional olefin monomer A2 was added, 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2Is used as a carrier and contains 2.3wt percent of Ti, 9.6wt percent of dibutyl phthalate as an internal electron donor and 1.7wt percent of diethyl phthalate), and the reaction is carried out for 15 minutes at 70 ℃.
796g of silicon dioxide and 400g of hexane solution are added into a batching tank, the mixture is added into the polymerization reaction kettle by a screw pump after being uniformly stirred, the feeding speed of the screw pump is controlled to be 20g/min, and the reaction kettle is stirred and reacted for 3 hours at room temperature at the stirring speed of 100 rpm. The product was collected and dried to yield 1126g of product.
The mass content of the propane-butadiene copolymer in the product is 29.3 wt%, and the mass content of the silicon dioxide is 70.7 wt%; in the propane-butadiene copolymer, the propylene content was 51.1 mol%, the 1-butene content was 41.3 mol%, the content of the functional monomer A2 was 7.6 mol%, and the basic properties of the polymer are shown in Table 1.
Example 4
Into a 2L reactor, 250g of propylene and 250g of 1-butene were charged, 10mol of the functional olefin monomer B1 was added, 40mL of 1.0mol/L methylaluminoxane solution and 20. mu. mol of the metallocene catalyst C were added under stirring2H4(Ind)2ZrCl2The reaction was carried out at 80 ℃ for 0.5 hour.
300g of silicon dioxide and 150g of hexane solution are added into a batching tank, stirred evenly and then added into the polymerization reaction kettle by a screw pump, the feeding speed of the screw pump is controlled to be 10g/min, and the reaction kettle is stirred and reacted for 2 hours at room temperature at the stirring speed of 100 rpm. The product was collected and dried to yield 667g of product.
The mass content of the propane-butadiene copolymer in the product is 55.0 wt%, and the mass content of the silicon dioxide is 45.0 wt%; in the propane-butadiene copolymer, the propylene content was 43.7 mol%, the 1-butene content was 43.5 mol%, the functional monomer B1 content was 12.8 mol%, and the basic properties of the polymer are shown in Table 1.
Example 5
Into a 2L reactor, 250g of propylene and 250g of 1-butene were charged, 1.5mol of a functional olefin monomer B2 was added, 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2As a carrier, 2.7 wt% of Ti and 10.5 wt% of internal electron donor dibutyl phthalate) and reacting for 1 hour at 70 ℃.
70g of silicon dioxide and 50g of hexane solution are added into a batching tank, the mixture is added into the polymerization reaction kettle by a screw pump after being uniformly stirred, the feeding speed of the screw pump is controlled to be 10g/min, and the reaction kettle is stirred and reacted for 2 hours at room temperature at the stirring speed of 150 rpm. The product was collected and dried to yield 400g of product.
The mass content of the propane-butadiene copolymer in the product is 82.2 wt%, and the mass content of the silicon dioxide is 17.8 wt%; in the propylene-butadiene copolymer, the propylene content was 53.9 mol%, the 1-butene content was 40.1 mol%, the functional monomer B2 content was 6.0 mol%, and the basic properties of the polymer are shown in Table 1.
Example 6
In a 2L reaction kettle350g of propylene and 150g of 1-butene were added, 1.5mol of a functional olefin monomer B2 was added, 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2Is used as a carrier, contains 2.3wt percent of Ti, 9.6wt percent of dibutyl phthalate as an internal electron donor, and 1.7wt percent of diethyl phthalate), and reacts at the temperature of 70 ℃ for 0.5.
100g of silicon dioxide and 50g of hexane solution are added into a batching tank, the mixture is added into the polymerization reaction kettle by a screw pump after being uniformly stirred, the feeding speed of the screw pump is controlled to be 20g/min, and the reaction kettle is stirred and reacted for 2 hours at room temperature at the stirring speed of 100 rpm. The product was collected, washed and dried to yield 450g of product.
The mass content of the propane-butadiene copolymer in the product is 77.3 wt%, and the mass content of the silicon dioxide is 22.7 wt%; in the propylene-butadiene copolymer, the propylene content was 75.1 mol%, the 1-butene content was 19.7 mol%, the functional monomer B2 content was 5.2 mol%, and the basic properties of the polymer are shown in Table 1.
Example 7
In a 2L reactor, 150g of propylene and 350g of 1-butene were charged, 1.5mol of a functional olefin monomer C was charged, 10mL of a 1.0mol/L triethylaluminum solution and 0.03g of a Ziegler-Natta catalyst (as MgCl) were added under stirring2As a carrier, 2.7 wt% of Ti and 10.5 wt% of internal electron donor dibutyl phthalate) and reacting for 2 hours at 70 ℃.
100g of silicon dioxide and 50g of hexane solution are added into a batching tank, the mixture is added into the polymerization reaction kettle by a screw pump after being uniformly stirred, the feeding speed of the screw pump is controlled to be 20g/min, and the reaction kettle is stirred and reacted for 1.5 hours at room temperature at the stirring speed of 100 rpm. The product was collected and dried to yield 540g of product.
The mass content of the propane-butadiene copolymer in the product is 81.5 wt%, and the mass content of the silicon dioxide is 18.5 wt%; in the propylene-butadiene copolymer, the propylene content was 19.8 mol%, the 1-butene content was 75.5 mol%, the functional monomer C content was 4.7 mol%, and the basic properties of the polymer are shown in Table 1.
The product is dissolved in boiling dimethylbenzene and then filtered while hot, the content of soluble substances is almost 0, and most of the propyl-butyl copolymer is chemically linked with silica particles and is in insoluble components which can be collected. The result shows that Si-Cl of the polymer chain side group of the propane-butane copolymer reacts with a large amount of Si-OH existing on the surface of the silicon dioxide particles, so that the polymer is combined with the silicon dioxide particles through chemical bonds, and the problems of compatibility between the silicon dioxide and the propane-butane copolymer and the dispersion stability of the silicon dioxide particles in the propane-butane copolymer are fundamentally solved. Meanwhile, the rigidity of the propylene-butadiene copolymer can be obviously improved by the silicon dioxide, which shows that the Young modulus of the polymer is obviously improved compared with that of the propylene-butadiene copolymer without the silicon dioxide, and the elongation at break is reduced to some extent due to the enhanced rigidity of the material, as shown in the data in the table 1.
FIG. 1 is a scanning electron micrograph of the quenched section of the composite of example 1, which shows that the granular silica is uniformly distributed in the propylene-butadiene copolymer, and it can be seen from the 6000 times magnified photograph that the copolymer is firmly attached to the surface of the silica particles with a diameter of about 20 μm, and the boundaries are very fuzzy, which indicates that the action force of the propylene-butadiene copolymer and the silica linked by chemical bonds is very strong.
The copolymer is very strong with silica.
TABLE 1 Polymer composition and Properties tabulation
Claims (12)
1. The composite of the silicon dioxide and the propane-butane copolymer is characterized in that the mass content of the propane-butane copolymer is 5-99%, the mass content of the silicon dioxide is 1-95%, the propane-butane copolymer is a copolymer formed by polymerizing propylene, 1-butene and a functional olefin monomer, wherein the molar content of a propylene unit is 5-95%, the molar content of a 1-butene unit is 5-95%, and the molar content of a functional olefin monomer unit is 0.01-50%;
the functional olefin monomer has the structure of
Wherein R is1And R2Which may be the same or different, is selected from the group consisting of Cl, methyl, ethyl, isopropyl, methoxy, ethoxy, isopropoxy; n is an integer of 1 to 12.
2. The composite of silica and a propylene-butadiene copolymer according to claim 1, wherein the silica is a particulate silica having a particle size in the range of 0.05 to 50 μm, preferably in the range of 0.1 to 20 μm.
3. A process for preparing a composite of silica and a propylene copolymer as defined in claim 1, which comprises the steps of:
(1) adding 1-butene, a functional olefin monomer, a propylene monomer and a cocatalyst into a polymerization reactor, and finally adding a main catalyst to perform polymerization reaction, wherein the mass ratio of the added 1-butene to the propylene is 1-10000: 100, the ratio of the added functional olefin monomer to the sum of the mass of the added propylene and the mass of the added 1-butene is 0.01-5: 1, the polymerization temperature is 0-100 ℃, the polymerization pressure is 0.2-6 MPa, and the polymerization time is 0.1-6 hours;
(2) preparing silicon dioxide slurry, wherein the mass ratio of silicon dioxide to organic solvent is 0.1-10: 1;
(3) adding the silicon dioxide slurry obtained in the step (2) into the polymerization product obtained in the polymerization reactor obtained in the step (1), controlling the stirring speed of the polymerization reactor to be 50-500 rpm, and controlling the mass ratio of silicon dioxide to polymer to be 0.01-19: 1, the mass of the silicon dioxide slurry added at the rate of one minute is 1-10% of the mass of the polymerization product in the step (1) in the reactor; after the addition is finished, reacting for 0.1-5 hours; and removing the residual unreacted 1-butene and propylene monomers after the reaction is finished to obtain the compound of the silicon dioxide and the propane-butadiene copolymer.
4. The method for preparing a composite of silica and a propylene copolymer according to claim 3, wherein the main catalyst is selected from a Ziegler-Natta catalyst or a metallocene catalyst, and the cocatalyst is selected from an alkylaluminum compound or an alkylaluminoxane compound; when the main catalyst adopts a Ziegler-Natta catalyst, the cocatalyst is selected from alkyl aluminum compounds; when the main catalyst is metallocene catalyst, the cocatalyst is selected from alkyl aluminoxane compounds.
5. A process for the preparation of a composite of silica and a propylene copolymer according to claim 4, wherein the Ziegler-Natta catalyst is a transition metal catalyst supported on a magnesium halide, the transition metal being chosen from Ti and V.
6. The method of claim 4, wherein the Ziegler-Natta catalyst comprises an internal electron donor component selected from the group consisting of diethyl succinate, dibutyl adipate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, 2-diisobutyl-1, 3-dimethoxypropane, and 9, 9-bis (methoxymethyl) fluorene.
7. The method for preparing a silica and propane-butadiene copolymer composite according to claim 4, wherein the metallocene catalyst is a transition metal-pi bond compound having a transition metal of Ti, Zr or Hf as a central atom.
8. The method for preparing a composite of silica and a propylene copolymer as claimed in claim 7, wherein the transition metal-pi-bond compound having Ti, Zr or Hf as a central atom is selected from C2H4(Me4Cp)2MCl2，C2H4(Ind)2MCl2，C2H4(2,4,7-Me3-Ind)2MCl2，Me2Si(Flu)2MCl2，Me2SiCH2(Ind)2MCl2，Me2Si(2-MeInd)2MCl2，Me2Si(2,5-Me-Cp)2MCl2，Me2Si(4,7-Me2-Ind)2MCl2，Me2Si(2-Me-4-Naph-Ind)2ZrCl2Where Me is methyl, Ph is phenyl, Cp is cyclopentadienyl, Ind is indenyl, H4Ind ═ 4,5,6, 7-tetrahydroindene, Flu ═ fluorenyl, Naph ═ naphthyl, and M is selected from Ti, Zr, or Hf.
9. The method for preparing a composite of silica and a copolymer of propane and butane according to claim 4, wherein the alkylaluminum is a trialkylaluminum or a mixture of a trialkylaluminum and an alkylaluminum halide or an alkylaluminum polyhalide.
10. The method for preparing a composite of silica and a propane-butadiene copolymer according to claim 9, wherein the trialkylaluminum is at least one selected from the group consisting of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and trialkylaluminum.
11. The method for preparing a complex of silica and a propane-butadiene copolymer according to claim 4, wherein the alkylaluminoxane is at least one selected from methylaluminoxane and isobutylaluminoxane.
12. The method for preparing a composite of silica and a propylene copolymer according to claim 3, wherein the amount of the co-catalyst added is, in terms of molar ratio of Al to Ti in the Ziegler-Natta catalyst or V, Al to M in the metallocene catalyst, Al: ti or V is 10-20000; al: m is 10-20000; m is selected from Ti, Zr or Hf.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910707185.2A CN112300495A (en) | 2019-08-01 | 2019-08-01 | Silicon dioxide and propane-butadiene copolymer compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910707185.2A CN112300495A (en) | 2019-08-01 | 2019-08-01 | Silicon dioxide and propane-butadiene copolymer compound and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112300495A true CN112300495A (en) | 2021-02-02 |
Family
ID=74485858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910707185.2A Pending CN112300495A (en) | 2019-08-01 | 2019-08-01 | Silicon dioxide and propane-butadiene copolymer compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112300495A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116572603A (en) * | 2023-07-13 | 2023-08-11 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266641A (en) * | 1989-10-06 | 1993-11-30 | Mitsui Toatsu Chemicals, Inc. | Butene-1 copolymers and resin compositions containing the same |
| CN107698703A (en) * | 2017-10-31 | 2018-02-16 | 大连理工大学 | Butylene copolymer of a kind of propylene/1 and its preparation method and application |
| JP2018178006A (en) * | 2017-04-17 | 2018-11-15 | 三井化学株式会社 | Thermoplastic elastomer composition, and application and manufacturing method thereof |
| CN108892748A (en) * | 2018-06-13 | 2018-11-27 | 大连理工大学 | Silica and EP rubbers compound and preparation method thereof |
-
2019
- 2019-08-01 CN CN201910707185.2A patent/CN112300495A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266641A (en) * | 1989-10-06 | 1993-11-30 | Mitsui Toatsu Chemicals, Inc. | Butene-1 copolymers and resin compositions containing the same |
| JP2018178006A (en) * | 2017-04-17 | 2018-11-15 | 三井化学株式会社 | Thermoplastic elastomer composition, and application and manufacturing method thereof |
| CN107698703A (en) * | 2017-10-31 | 2018-02-16 | 大连理工大学 | Butylene copolymer of a kind of propylene/1 and its preparation method and application |
| CN108892748A (en) * | 2018-06-13 | 2018-11-27 | 大连理工大学 | Silica and EP rubbers compound and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张丹枫: "《烯烃聚合》", 30 September 2014 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116572603A (en) * | 2023-07-13 | 2023-08-11 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
| CN116572603B (en) * | 2023-07-13 | 2023-09-22 | 浙江葆润应用材料有限公司 | Composite heat insulation material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1066329B1 (en) | Polymeric supported catalysts for olefin polymerization | |
| JP4652343B2 (en) | Supported metallocene catalyst, process for producing the same, and process for producing polyolefin using the same | |
| US5492985A (en) | Polymerization processes | |
| JP2989512B2 (en) | Spray-dried and filled metallocene catalyst composition for use in polyolefin production | |
| JP5671750B2 (en) | Method for producing supported metallocene catalyst and method for producing polyolefin using the same | |
| US7662894B2 (en) | Polymer supported metallocene catalyst composition for polymerizing olefins | |
| HU217575B (en) | Catalyst components the polymerization of olefin catalyst containing them, process for the polymerization of olefins, polymers produced thereby and the shaped articles | |
| CN105473601B (en) | Metallocene compound, comprising its carbon monoxide-olefin polymeric and using it prepare the method for olefin polymer | |
| KR100240519B1 (en) | Chealate catalyst for polymerising olefin | |
| CZ20014646A3 (en) | Process for preparing alkoxide complexes of magnesium/transient metal and polymerization catalysts prepared from these complexes | |
| JP2002538237A (en) | Metallocene compounds and olefin polymerization using the same | |
| WO2019237582A1 (en) | Complex of silica and ethylene propylene rubber and preparation method therefor | |
| JP2001122886A (en) | Biscyclopentadienyl compound bridged with single carbon and its metallocene complex | |
| CN106661072A (en) | Metallocene compound, catalyst composition comprising same, and method for preparing olefin-based polymer using same | |
| US6500906B1 (en) | Olefin polymerization chelate catalyst and olefin polymerization method using the same | |
| US6992034B2 (en) | Catalyst component for olefin polymerization | |
| CN112300495A (en) | Silicon dioxide and propane-butadiene copolymer compound and preparation method thereof | |
| US11702487B2 (en) | Process for preparing propylene polymers | |
| JP4779179B2 (en) | Method for producing ethylene polymerization catalyst | |
| US6818713B1 (en) | Process for making polyethylene | |
| US6426313B2 (en) | Polymeric supported catalysts for olefin polymerization | |
| JPH111489A (en) | Metallocene compound and polymerization using the same | |
| US6861487B2 (en) | Catalyst precursor for the polymerization of olefins and polymerization process using the same | |
| JPH07188323A (en) | Catalytic composition for polymerization of alpha olefin | |
| JPH0343404A (en) | Propylene polymerization catalyst and polymerization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210202 |
|
| WD01 | Invention patent application deemed withdrawn after publication |