CN112646083B - Preparation method of toughening agent of polystyrene - Google Patents
Preparation method of toughening agent of polystyrene Download PDFInfo
- Publication number
- CN112646083B CN112646083B CN201910969163.3A CN201910969163A CN112646083B CN 112646083 B CN112646083 B CN 112646083B CN 201910969163 A CN201910969163 A CN 201910969163A CN 112646083 B CN112646083 B CN 112646083B
- Authority
- CN
- China
- Prior art keywords
- butadiene
- styrene
- nickel
- polystyrene
- toughening agent
- 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.)
- Active
Links
Images
Classifications
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- 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
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
-
- 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
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A preparation method of a toughening agent of polystyrene belongs to the technical field of polymer synthesis. The method comprises the following steps: 1) preparation of liquid butadiene-styrene copolymer: carrying out anionic polymerization reaction in a polymerization solvent by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator and butadiene and styrene as monomers to prepare a butadiene-styrene copolymer; 2) under the condition of nickel-aluminum catalyst, butadiene and butadiene-styrene copolymer are polymerized in organic solvent, and after polymerization, terminator is added to prepare butadiene-styrene grafted nickel butadiene rubber glue solution. The toughening agent of the polystyrene comprises the following components: the butadiene-styrene grafted nickel butadiene rubber has a monomer conversion rate of more than or equal to 80%, a molecular weight of 72000-110000, a molecular weight distribution of 3.5-6.5 and a 1,4 structure content of more than or equal to 95%. The polystyrene toughening agent has good compatibility with polystyrene, can obviously improve the toughness of the polystyrene, and has good strength retention rate.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a preparation method of a toughening agent for polystyrene.
Background
Polystyrene, also known as PS resin, is a brittle, glass-like thermoplastic resin material. Polystyrene has the advantages of transparency, low price, rigidity, insulation, good printing property, easy processing and forming and the like, is widely applied to the light industry market, such as daily dress sulfonic, illumination indication, packaging and the like, and is one of large varieties of synthetic resins widely applied at present. The material is a good insulating material and a heat insulation material in the electrical aspect, and can be used for manufacturing various instrument shells, lamp shades, optical chemical instrument parts, transparent films, capacitor dielectric layers and the like. The traditional polystyrene product has the advantages of extremely high transparency, light transmittance of over 90, good electrical insulation performance, easy coloring, good processing fluidity, good rigidity, good chemical corrosion resistance, low price and the like, and the glass transition temperature of the polystyrene is higher by about 80-100 ℃, so the polystyrene product is brittle and easy to generate stress embrittlement. Currently, in order to improve the impact properties and increase the toughness of polystyrene, polystyrene and elastomers are copolymerized to form industrial products of impact-resistant polystyrene, typically styrene-butadiene copolymers or hydrogenated styrene-butadiene copolymers. The method has complex synthesis and higher cost.
Patent CN 106188546a "polystyrene impact-resistant toughening modifier and preparation method thereof" proposes that polyorganosiloxane is the best elastomer material with the best low temperature resistance at present, the main chain Si-O bond has not only high bond energy but also good flexibility, and a small amount of polydimethylsiloxane can obviously improve the impact resistance and toughness of polystyrene. However, since the compatibility between silicone and PS is poor, tensile strength and flexural strength are significantly reduced while the impact strength is improved.
At present, a toughening agent which can solve the problem of high brittleness of polystyrene, has tensile strength and bending strength which are not reduced as much as possible and has lower production cost is urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the preparation method of the polystyrene toughening agent is provided, the polystyrene toughening agent has good compatibility with polystyrene, the toughness of the polystyrene can be obviously improved, and the strength retention rate is good.
The invention is realized by the following technical scheme: the preparation method of the toughening agent of the polystyrene comprises the following steps:
1) preparation of butadiene-styrene copolymer: carrying out anionic polymerization reaction in a polymerization solvent by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator and butadiene and styrene as monomers to prepare a butadiene-styrene copolymer (liquid);
2) preparing butadiene-styrene grafted nickel butadiene rubber liquid: under the condition of nickel catalyst, butadiene and butadiene-styrene copolymer are polymerized in organic solvent, and after the polymerization reaction is finished, terminator is added to prepare butadiene-styrene grafted nickel butadiene rubber glue solution.
The butadiene-styrene copolymer in the step 1) has the number average molecular weight of 6500-26000, the molecular weight distribution of 1.0-1.2, and the 1, 2-structure content in a butadiene structural unit of the butadiene-styrene copolymer is 63.0-66% by mass.
The butadiene-styrene copolymer in the step 1) has the number average molecular weight of 6700-25000 and the molecular weight distribution of 1.1, and the 1, 2-structure content in a butadiene structural unit is 63.6-65.5 mass percent.
The polymerization solvent in the step 1) is one or a mixture of more than two of n-pentane, n-hexane, n-heptane and n-octane in any proportion.
The mol ratio of n-butyllithium to butadiene in the step 1) is 0.02, the mol ratio of tetrahydrofuran to butadiene is 5, and the mass ratio of butadiene to styrene is 7: 3.
the reaction conditions of the anionic polymerization reaction in the step 1) are as follows: the polymerization temperature is 55-65 ℃, the polymerization pressure is 0.1-0.4 MPa, and the polymerization time is 2-6 h.
The nickel catalyst in the step 2) contains diethyl ether complex of nickel naphthenate, aluminum alkyl, n-octanol and boron trifluoride; the molar ratio of the diethyl ether complex of the nickel naphthenate, the alkyl aluminum, the n-octanol and the boron trifluoride is 1: 10-20: 12-40: 12 to 40. Preferably, the molar ratio of the nickel naphthenate, the alkyl aluminum, the n-octanol and the boron trifluoride diethyl etherate complex is 1: 12: 15: 15.
The mass ratio of the butadiene-styrene copolymer in the step 2) to the butadiene is 5%.
The toughening agent of the polystyrene is butadiene styrene grafted nickel butadiene rubber, the monomer conversion rate (abbreviated as C%) is more than or equal to 80%, the molecular weight is 72000-110000, the molecular weight distribution is 3.5-6.5, and the 1,4 structure content is more than or equal to 95% by mass percent.
Preferably, the butadiene-styrene grafted nickel butadiene rubber has a monomer conversion rate of more than or equal to 98%, a molecular weight of 73000-109000, a molecular weight distribution of 3.6-6.1, and a 1,4 structure of 97.4-99% by mass.
The present invention is described in detail as follows:
the anionic polymerization reaction in the step 1) and the polymerization reaction in the step 2) are carried out under the protection of inert gas.
The preparation method also comprises the step 3) of precipitating, washing and drying the butadiene-styrene grafted nickel butadiene rubber glue solution.
Preferably, in the butadiene-styrene grafted nickel-based butadiene rubber: the mass content of the butylbenzene grafting is more than or equal to 5 percent; mooney viscosity ML (1 + 4) 100℃ ：30～60。
The molar ratio of the butadiene-styrene copolymer in the step 2) to the nickel naphthenate in the nickel-based catalyst is 2.5-3.0.
The nickel-based catalyst in the step 2) comprises a nickel-aluminum catalyst aging solution and an n-octanol-boron aging solution. Adding the nickel-aluminum catalyst aging solution and the n-octanol-boron aging solution in sequence in the polymerization reaction of the step 2).
The preparation method of the nickel-aluminum catalyst aging liquid comprises the following steps: under the protection of inert gas, nickel naphthenate and aluminum alkyl (Al for short) are contacted in an organic solvent and aged, wherein the molar ratio of Al/Ni is 1: 10-20 ℃, wherein the aging temperature is 40-50 ℃, and the aging time is 15-30 min; preferably, the inert gas is nitrogen, and the organic solvent used during aging is n-hexane.
The preparation method of the n-octanol-boron aging liquid comprises the following steps: under the protection of inert gas, boron trifluoride diethyl etherate (B for short) and n-octanol are contacted and aged in an organic solvent, wherein the molar ratio of B to n-octanol is 1: 1, aging at 40-50 ℃ for 15-30 min to obtain the product; preferably, the inert gas is nitrogen, and the organic solvent used during aging is n-hexane.
The organic solvent in the step 2) is one or a mixture of more than two of n-pentane, n-hexane, cyclohexane, n-heptane and n-octane in any proportion.
The polymerization reaction conditions in the step 2) are as follows: the polymerization temperature is 50-70 ℃, the polymerization pressure is 0.1-0.4 MPa, and the polymerization time is 2-6 h.
The terminating agent in the step 2) is an ethanol solution of 2, 6-di-tert-butylhydroquinone with the mass concentration of 3 wt%.
Compared with the prior art, the preparation method of the toughening agent for polystyrene has the beneficial effects that:
1. the toughening agent of the polystyrene has good compatibility with the polystyrene. The butadiene-styrene copolymer is used as a grafting agent, and the prepared butadiene-styrene macromolecule grafted butadiene-styrene toughening agent contains a styrene chain segment, so that the problem of poor compatibility of other toughening agents and PS is solved.
2. The toughening agent of the polystyrene is butadiene styrene grafted nickel butadiene rubber, and can obviously improve the toughness of the polystyrene. The addition of the butadiene chain segment in the butadiene-styrene copolymer can ensure that a polybutadiene aggregate exists in a system in a sea island structure, and the sea island structure has stronger capacity of absorbing and dissipating energy, so that the toughness of the PS blend can be obviously improved. While having a high strength retention.
3. The preparation method of the polystyrene toughening agent is simple and easy to implement, can be used for producing the nickel-based butadiene rubber on the conventional device for producing the nickel-based butadiene rubber, and is low in production cost.
Drawings
FIG. 1 dynamic viscosity diagrams of styrene-butadiene grafted nickel-based butadiene rubber at different shear rates for examples 1 to 4 and comparative example 1, which are used to illustrate the degree of grafting in comparative example 1 and example.
FIG. 2 is an electron micrograph of the PC blends of example 6 and comparative example 2.
Detailed Description
Examples 1 to 4 are specific embodiments of a method for preparing a toughening agent for polystyrene according to the present invention. Of these, example 2 is the most preferred example. Comparative examples 1-2 are comparative examples designed by the applicant.
The raw materials used in the examples and comparative examples are as follows:
styrene-butadiene rubber (SBR) used in the comparative example, Chinesemedicine Qilu petrochemical company 1502.
N-butyllithium, analytical grade, Aladdin reagent, Inc.
Tetrahydrofuran, analytically pure, Tianjin Fuyu Fine chemical Co., Ltd.
Butadiene, technical grade, china petrochemical, zipu petrochemical company.
Styrene, technical grade, china petrochemicals, qilu petrochemical company.
Polystyrene (PS resin), Ningbo Taiwan GP-535N transparent polystyrene.
Nickel naphthenate, analytically pure, alatin reagent, inc.
Alkylaluminum, analytical grade, Aladdin reagent, Inc.
N-octanol, analytical grade, Aladdin reagent, Inc.
Boron trifluoride, analytical grade, Aladdin reagent, Inc.
Diethyl ether, analytical grade, Aladdin reagent, Inc.
The preparation method of the nickel-aluminum catalyst aging liquid used in the examples comprises the following steps: sequentially adding nickel naphthenate (Ni) n-hexane solution and triisobutylaluminum (Al) into a catalyst preparation kettle under the protection of inert gas, wherein the molar ratio of Al/Ni is 1: and (3) aging for 10-20 min at 45 ℃ to obtain the product.
The preparation method of the n-octanol-boron aging liquid used in the examples comprises the following steps: adding boron trifluoride diethyl etherate (B for short) into n-hexane solution of n-octanol, wherein the molar ratio of B/n-octanol is 1: 1, aging at 40 ℃ for 15 min to obtain the product.
Examples the properties of the butadiene-styrene copolymer obtained in step 1) are shown in the following table:
TABLE 1 examples 1-4 Properties of butadiene-styrene copolymers
Example 1
1) Preparation of butadiene-styrene copolymer: under the protection of nitrogen, carrying out anionic polymerization reaction in normal hexane by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator and butadiene and styrene as monomers, wherein the polymerization temperature is 60 ℃, the polymerization pressure is 0.1-0.4 MPa, and the polymerization time is 5h to prepare a butadiene-styrene copolymer; wherein the mol ratio of n-butyllithium to butadiene is 0.02, the mol ratio of tetrahydrofuran to butadiene is 5, and the mass ratio of butadiene to styrene is 7: 3;
2) preparing butadiene-styrene grafted nickel butadiene rubber liquid: in a 30ml polymerization tube which is subjected to vacuum pumping and high-purity nitrogen replacement for three times, uniformly mixing a solvent n-hexane and a monomer butadiene in the polymerization tube (the monomer concentration [ M ] =0.14 g/ml), adding a butadiene-styrene copolymer, and sequentially adding a nickel-aluminum catalyst aging solution and an n-octanol-boron aging solution, wherein the polymerization temperature is 60 ℃, the polymerization pressure is 0.1 MPa-0.4 MPa, and the polymerization time is 6 h; after the polymerization reaction is finished, adding 1.5mL of ethanol solution of 2, 6-di-tert-butylhydroquinone with the mass concentration of 3wt% for termination reaction to prepare butadiene-styrene grafted nickel butadiene rubber glue solution; the mass ratio of the butadiene-styrene copolymer to the butadiene is 5 percent; the molar ratio of the diethyl ether complex of butadiene-styrene copolymer, nickel naphthenate, aluminum alkyl, n-octanol and boron trifluoride was 2.5: 1: 10: 17: 17;
3) and precipitating, washing and drying the butadiene styrene grafted nickel butadiene rubber glue solution.
Example 2
1) Preparation of butadiene-styrene copolymer: under the protection of nitrogen, carrying out anionic polymerization reaction in n-hexane by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator and butadiene and styrene as monomers, wherein the polymerization temperature is 55 ℃, the polymerization pressure is 0.1-0.4 MPa, and the polymerization time is 4h to prepare a butadiene-styrene copolymer; wherein the mol ratio of n-butyllithium to butadiene is 0.02, the mol ratio of tetrahydrofuran to butadiene is 5, and the mass ratio of butadiene to styrene is 7: 3;
2) preparing butadiene-styrene grafted nickel butadiene rubber liquid: in a 30ml polymerization tube which is subjected to vacuum pumping and high-purity nitrogen replacement for three times, uniformly mixing a solvent n-hexane and a monomer butadiene in the polymerization tube (the monomer concentration [ M ] =0.14 g/ml), adding a butadiene-styrene copolymer, and sequentially adding a nickel-aluminum catalyst aging solution and an n-octanol-boron aging solution, wherein the polymerization temperature is 55 ℃, the polymerization pressure is 0.1 MPa-0.4 MPa, and the polymerization time is 6 h; after the polymerization reaction is finished, adding 1.5mL of ethanol solution of 2, 6-di-tert-butylhydroquinone with the mass concentration of 3wt% for termination reaction to prepare butadiene-styrene grafted nickel butadiene rubber glue solution; the mass ratio of the butadiene-styrene copolymer to the butadiene is 5 percent; the molar ratio of the diethyl ether complex of butadiene-styrene copolymer, nickel naphthenate, aluminum alkyl, n-octanol and boron trifluoride is 3: 1: 12: 15: 15;
3) and precipitating, washing and drying the butadiene styrene grafted nickel butadiene rubber glue solution.
Example 3
1) Preparation of butadiene-styrene copolymer: under the protection of nitrogen, carrying out anionic polymerization reaction in normal hexane by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator and butadiene and styrene as monomers, wherein the polymerization temperature is 65 ℃, the polymerization pressure is 0.1-0.4 MPa, and the polymerization time is 2h to prepare a butadiene-styrene copolymer; wherein the mol ratio of n-butyllithium to butadiene is 0.02, the mol ratio of tetrahydrofuran to butadiene is 5, and the mass ratio of butadiene to styrene is 7: 3;
2) preparing butadiene-styrene grafted nickel butadiene rubber liquid: in a 30ml polymerization tube which is subjected to vacuum pumping and high-purity nitrogen replacement for three times, uniformly mixing a solvent n-hexane and a monomer butadiene in the polymerization tube (the monomer concentration [ M ] =0.14 g/ml), adding a butadiene-styrene copolymer, and sequentially adding a nickel-aluminum catalyst aging solution and an n-octanol-boron aging solution, wherein the polymerization temperature is 55 ℃, the polymerization pressure is 0.1 MPa-0.4 MPa, and the polymerization time is 5 hours; after the polymerization reaction is finished, adding 1.5mL of ethanol solution of 2, 6-di-tert-butylhydroquinone with the mass concentration of 3wt% for termination reaction to prepare butadiene-styrene grafted nickel butadiene rubber glue solution; the mass ratio of the butadiene-styrene copolymer to the butadiene is 5 percent; the molar ratio of the diethyl ether complex of butadiene-styrene copolymer, nickel naphthenate, aluminum alkyl, n-octanol and boron trifluoride was 2.8: 1: 20: 37: 37;
3) and precipitating, washing and drying the butadiene styrene grafted nickel butadiene rubber glue solution.
Example 4
1) Preparation of butadiene-styrene copolymer: under the protection of nitrogen, carrying out anionic polymerization reaction in normal hexane by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator and butadiene and styrene as monomers, wherein the polymerization temperature is 60 ℃, the polymerization pressure is 0.1-0.4 MPa, and the polymerization time is 5 hours to prepare a butadiene-styrene copolymer; wherein the mol ratio of n-butyllithium to butadiene is 0.02, the mol ratio of tetrahydrofuran to butadiene is 5, and the mass ratio of butadiene to styrene is 7: 3;
2) preparing butadiene-styrene grafted nickel butadiene rubber liquid: in a 30ml polymerization tube which is subjected to vacuum pumping and high-purity nitrogen replacement for three times, uniformly mixing a solvent n-hexane and a monomer butadiene in the polymerization tube (the monomer concentration [ M ] =0.14 g/ml), adding a butadiene-styrene copolymer, and sequentially adding a nickel-aluminum catalyst aging solution and an n-octanol-boron aging solution, wherein the polymerization temperature is 65 ℃, the polymerization pressure is 0.1 MPa-0.4 MPa, and the polymerization time is 2 h; after the polymerization reaction is finished, adding 1.5mL of ethanol solution of 2, 6-di-tert-butylhydroquinone with the mass concentration of 3wt% for termination reaction to prepare butadiene-styrene grafted nickel butadiene rubber glue solution; the mass ratio of the butadiene-styrene copolymer to the butadiene is 5 percent; the molar ratio of the diethyl ether complex of butadiene-styrene copolymer, nickel naphthenate, aluminum alkyl, n-octanol and boron trifluoride was 2.9: 1: 16: 20: 20;
3) and precipitating, washing and drying the butadiene styrene grafted nickel butadiene rubber glue solution.
Example 5
The blending process of 70 parts of PS resin and 30 parts of the toughening agent in the embodiment 1 comprises the following steps: the PS resin was mixed with the toughener of example 1 on a two-roll mill at 150 ℃ for 8 min. The prepared sheets were stacked together and pressed at 180 ℃ in a press vulcanizer to prepare a 2.0mm thick sample of the PS blend.
Example 6
The blending process and the raw material ratio are the same as those of the example 5, except that the toughening agent in the example 1 is replaced by the toughening agent in the example 2.
Example 7
The blending process and the raw material ratio are the same as those of the example 5, except that the toughening agent in the example 1 is replaced by the toughening agent in the example 3.
Example 8
The blending process and the raw material ratio are the same as those of the example 5, and the difference is that the toughening agent in the example 1 is replaced by the toughening agent in the example 4.
Comparative example 1
This comparative example is a blank control and the PS resin is pressed on a press at 180 ℃ to form 2.0mm thick plaques.
Comparative example 2
The blending process and the raw material ratio are the same as those of the example 5, except that the toughening agent in the example 1 is replaced by SBR.
Performance testing
Firstly, testing the performance of the toughening agent:
the examples 1 to 4 were examined, and the examination data are shown in Table 1. The detection method comprises the following steps:
1. the method for measuring the viscosity of the glue solution comprises the following steps: the polymerization product was made into a solution of 2g/100ml using cyclohexane as solvent, and the torque α of the solution at different rotational speeds was measured at 25. + -. 0.2 ℃ using a rotational viscometer. The dynamic viscosity η (in pa.s) of the gel sample was calculated according to the following formula: τ = α × Z, η = τ/γ, Z is a rotation angle constant, τ is a shear stress, and γ is a shear rate.
2. The polybutadiene was characterized for weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) by Gel Permeation Chromatography (GPC), and standard curves were prepared with polystyrene standards; the viscosity data of the linear polymer and the graft polymer were measured by a gel chromatograph-laser light scattering instrument-on-line viscometer combination system.
3. The cis content and composition of the polymer were characterized using Fourier Infrared (FT-IR). The polymer was dissolved in toluene and measured on a Nicolet FT-IR-Magna-750 infrared spectrometer by a membrane coating method.
4. Measuring molecular weight by polybutadiene viscosity method: the polymer was dissolved in toluene to give a 30mg/25ml solution, and the time t0 for pure toluene to flow out and the time t for the solution to flow out were measured at 30. + -. 0.2 ℃ with an Ubbelohde viscometer, from which: [ eta ]]=3[(t/t 0 )1/3－1]C, calculating [ eta ] of the product](ii) a From the MHS equation: [ eta ]]=KMη α Obtaining the molecular weight; wherein the parameter K = 3.05X 10 in the MHS equation for polybutadiene under these conditions -4 m 3 /kg，α＝0.7255。
5. And (3) measuring the gel content: drying and cooling the clean 120-mesh nickel net in an oven twice at constant weight (W) 0 ) (ii) a 250mg (W) of polymer is weighed, dissolved in 50ml of toluene and left for 48 hours, filtered through a nickel screen and washed three times with toluene, the nickel screen is dried in a vacuum drying oven and twice (W) of constant weight 1 ). Calculating the gel content: GC ═ W 1 -W 0 )100%/ W。
TABLE 2 test results of examples 1 to 4 and comparative example 1
Secondly, testing the performance of the PS blend:
the comparative examples 1-2 and the examples 5-8 are tested, and the test data are recorded in the following table.
TABLE 3 test results of examples 5 to 8 and comparative examples 1 to 2
As is apparent from Table 3, the impact strength of the PS blend modified by the toughening agent of the present invention is greatly improved, and the increase is more significant compared with comparative example 2 in which SBR is used for toughening. The highest impact strength of example 6, with the highest grafting degree of the toughening agent, reaches 32.1 MPa. In comparative example 2, the graft toughening agent had a larger rubber island structure (see FIG. 2) because SBR was used in combination. When the material is subjected to bending deformation and stretching deformation, the rubber phase butadiene chains can have faster and more complete molecular chain orientation, so that the rubber phase butadiene chains can resist larger deformation and strength, and the bending strength and the stretching strength are high. The toughener used in example 6 has high grafting degree and a large content of styrene structural units, so that the compatibility of polystyrene and the toughener is good, and the mechanical property is better.
As can be seen from the dynamic viscosity diagram of the styrene-butadiene grafted nickel-based butadiene rubber under different shear rates in the attached figure 1, after the structural modifier is added, the molecular weight of the structural modifier is 1 multiplied by 10 4 The intrinsic viscosity of the polymer product is the lowest at the same molecular weight and the grafting degree of the polymer product is the highest.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the toughening agent for polystyrene is characterized by comprising the following steps:
1) preparation of butadiene-styrene copolymer: carrying out anionic polymerization reaction in a polymerization solvent by using n-butyllithium as an initiator, tetrahydrofuran as a structure regulator and butadiene and styrene as monomers to prepare a butadiene-styrene copolymer;
2) preparing butadiene-styrene grafted nickel butadiene rubber liquid: under the condition of nickel catalyst, butadiene and butadiene-styrene copolymer are polymerized in organic solvent, and after the polymerization reaction is finished, a terminator is added to prepare butadiene-styrene grafted nickel butadiene rubber glue solution;
the butadiene-styrene copolymer in the step 1) has the number average molecular weight of 6500-28000, the molecular weight distribution of 1.0-1.2, the 1, 2-structure content of 63.0-66%, and the mass ratio of butadiene to styrene is 7: 3;
the mass ratio of the butadiene-styrene copolymer in the step 2) to the butadiene is 5%.
2. The method for preparing a toughening agent for polystyrene according to claim 1, wherein: the butadiene-styrene copolymer in the step 1) has the number average molecular weight of 6700-26000, the molecular weight distribution of 1.1 and the 1, 2-structure content of 63.6-65.5%.
3. The method for preparing a toughening agent for polystyrene according to claim 1, wherein: the polymerization solvent in the step 1) is one or a mixture of more than two of n-pentane, n-hexane, n-heptane and n-octane in any proportion.
4. The method for preparing a toughening agent for polystyrene according to claim 1, wherein: the mol ratio of n-butyllithium to butadiene in the step 1) is 0.02, the mol ratio of tetrahydrofuran to butadiene is 5, and the mass ratio of butadiene to styrene is 7: 3.
5. the method for preparing a toughening agent for polystyrene according to claim 1, wherein: the reaction conditions of the anionic polymerization reaction in the step 1) are as follows: the polymerization temperature is 55-65 ℃, the polymerization pressure is 0.1-0.4 MPa, and the polymerization time is 2-6 h.
6. The method for preparing a toughening agent for polystyrene according to claim 1, wherein: the nickel catalyst in the step 2) contains diethyl ether complex of nickel naphthenate, aluminum alkyl, n-octanol and boron trifluoride; the molar ratio of the diethyl ether complex of the nickel naphthenate, the alkyl aluminum, the n-octanol and the boron trifluoride is 1: 10-20: 12-40: 12 to 40.
7. A toughening agent for polystyrene prepared by the preparation method of any one of claims 1 to 6, which is characterized in that: the butadiene styrene grafted nickel butadiene rubber is butadiene styrene grafted nickel butadiene rubber, the monomer conversion rate is more than or equal to 80%, the number average molecular weight is 72000-110000, the molecular weight distribution is 3.5-6.5, and the structural content of 1,4 is more than or equal to 95%.
8. The toughening agent for polystyrene according to claim 7, wherein: the butadiene-styrene grafted nickel butadiene rubber has a monomer conversion rate of more than or equal to 98%, a number average molecular weight of 73000-109000, a molecular weight distribution of 3.6-6.1, and a 1,4 structure of 97.4-99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910969163.3A CN112646083B (en) | 2019-10-12 | 2019-10-12 | Preparation method of toughening agent of polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910969163.3A CN112646083B (en) | 2019-10-12 | 2019-10-12 | Preparation method of toughening agent of polystyrene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112646083A CN112646083A (en) | 2021-04-13 |
| CN112646083B true CN112646083B (en) | 2022-08-12 |
Family
ID=75342961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910969163.3A Active CN112646083B (en) | 2019-10-12 | 2019-10-12 | Preparation method of toughening agent of polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112646083B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113429515B (en) * | 2021-07-09 | 2023-09-22 | 浙江众立合成材料科技股份有限公司 | Preparation method of viscosity-controllable liquid hydrocarbon polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258177A (en) * | 2005-10-06 | 2008-09-03 | Lg化学株式会社 | Graft copolymer and method for preparing the same |
| CN107722402A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of toughening agent composition and ABS resin and preparation method thereof |
| CN107793534A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of butadiene rubber |
-
2019
- 2019-10-12 CN CN201910969163.3A patent/CN112646083B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258177A (en) * | 2005-10-06 | 2008-09-03 | Lg化学株式会社 | Graft copolymer and method for preparing the same |
| CN107722402A (en) * | 2016-08-10 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of toughening agent composition and ABS resin and preparation method thereof |
| CN107793534A (en) * | 2016-08-30 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of preparation method of butadiene rubber |
Non-Patent Citations (1)
| Title |
|---|
| 丁苯接枝高乙烯基聚丁二烯及其与丁苯橡胶共混胶的性能研究;邓志峰;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》;20130415(第04期);第20页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112646083A (en) | 2021-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7064164B2 (en) | Transparent styrol-butadiene block copolymer mixtures | |
| JP3976505B2 (en) | Transparent impact resistance improved polystyrene based on styrene butadiene block copolymer, polymer mixture containing the same, method for producing and using the same | |
| US4335221A (en) | Preparation of mixtures of linear three-block copolymers, and moldings produced therefrom | |
| CN112646083B (en) | Preparation method of toughening agent of polystyrene | |
| CN101903409A (en) | Process for the preparation of a 1,3-butadiene and styrene copolymer containing a random section in its main chain followed by a block with a structure differentiated from the main chain, homopolymeric or copolymeric functionalized and the product obtained from this | |
| CN104628963B (en) | Polyisoprene, preparation method thereof and vulcanized rubber | |
| CN1138055A (en) | Process for preparing asymmetric radial polymers | |
| CN110387012A (en) | A kind of branching type functional solution polymerized butadiene styrene rubber and preparation method thereof | |
| CN110256631A (en) | Ternary atactic copolymer and its preparation method and application containing beta-myrcene | |
| CN1247631C (en) | Process for producing high cis-polybutadiene rubber | |
| CN111875720A (en) | Functionalized SEBS and preparation method thereof | |
| CN107286296B (en) | Application of butadiene-b-isoprene polymer | |
| CN113717336A (en) | Star block copolymer (SIBR-BR) n-C and preparation method thereof | |
| CN113831458A (en) | Preparation method of butyl rubber with medium Mooney viscosity and low saturation | |
| CN118047919A (en) | Monovinylarene and conjugated diene block copolymer composition, preparation method and application thereof | |
| CN114478950B (en) | Three-arm comb-shaped star-shaped branched butyl rubber and preparation method thereof, and preparation method of three-arm star-shaped nucleating agent | |
| CN114085434B (en) | Low cis-polybutadiene rubber, preparation method and application thereof, HIPS resin and preparation method thereof | |
| JP2020026467A (en) | Vulcanizate | |
| CN113717331B (en) | Star block copolymer (SIBR-BR) n-C ABS resin with ultrahigh impact strength and preparation method thereof | |
| CN113912798B (en) | Star block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and preparation method thereof | |
| CN113817112B (en) | Star-shaped block copolymer (SIBR-BR) n-C HIPS resin with ultrahigh impact strength and preparation method thereof | |
| CN111978447B (en) | Low cis-polybutadiene rubber, preparation method and application thereof, aromatic vinyl resin and preparation method thereof | |
| JP7380121B2 (en) | rubber composition | |
| Yu et al. | Poly [glycidyl methacrylate (GMA)/methylmethacrylate (MMA)‐b‐butadiene (B)‐b‐GMA/MMA] reactive thermoplastic elastomers: Synthesis and characterization | |
| CN108610457B (en) | Preparation method of silicon-containing high vinyl polybutadiene |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |