CN111978446A - Polybutadiene rubber, preparation method and application thereof, aromatic vinyl resin and preparation method thereof - Google Patents

Polybutadiene rubber, preparation method and application thereof, aromatic vinyl resin and preparation method thereof Download PDF

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CN111978446A
CN111978446A CN201910425475.8A CN201910425475A CN111978446A CN 111978446 A CN111978446 A CN 111978446A CN 201910425475 A CN201910425475 A CN 201910425475A CN 111978446 A CN111978446 A CN 111978446A
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molecular weight
weight component
polybutadiene rubber
coupling
number average
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CN111978446B (en
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李建成
徐林
王雪
赵姜维
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers 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
    • C08F136/04—Homopolymers 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
    • C08F136/06—Butadiene
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses polybutadiene rubber and a preparation method thereof, and aromatic vinyl resin adopting the polybutadiene rubber as a toughening agent and a preparation method thereof. The molecular weight of the polybutadiene rubber is in a four-peak distribution, the preparation method comprises the steps of polymerizing 1, 3-butadiene in an organic solvent in the presence of an organic lithium initiator and a structure regulator, contacting the obtained polymerization solution with a coupling agent to carry out coupling reaction, wherein the coupling agent is a four-functional group coupling agent, and the molar weight of the coupling agent is nCThe molar amount of the organolithium initiator is nI，2.8nI≥(nC×4)≥1.4nI. The preparation method obtains the polybutadiene rubber with the four-peak distribution through one-step coupling reaction, and the polybutadiene rubber used as the toughening agent of the aromatic vinyl resin can obviously improve the impact resistance of the aromatic vinyl resin and simultaneously can keep better glossiness.

Description

Polybutadiene rubber, preparation method and application thereof, aromatic vinyl resin and preparation method thereof
Technical Field
The invention relates to polybutadiene rubber, a preparation method and application thereof, and also relates to aromatic vinyl resin adopting the polybutadiene rubber as a toughening agent and a preparation method thereof.
Background
Conventional aromatic vinyl resins, for example: in the preparation of high impact polystyrene resin (HIPS resin), the rubber conventionally selected as the toughening agent may be low cis-polybutadiene rubber, high cis-polybutadiene rubber, butadiene-isoprene copolymer, solution-polymerized styrene-butadiene rubber, styrene-butadiene-styrene copolymer, and particularly, low cis-polybutadiene rubber and high cis-polybutadiene rubber are the most preferable. For low-temperature toughness resin, low cis-polybutadiene rubber is generally selected for toughening.
The molecular weight and the distribution of the toughened rubber have obvious influence on the impact resistance of the continuous body HIPS resin, and generally, the rubber molecular weight is too small, so that the toughening effect is poor; the rubber particle size is too concentrated, and the glossiness and the impact resistance of the resin are poor. In the selection of the toughening agent, rubbers with different particle sizes need to be matched, so that the rubbers with different particle sizes act synergistically to realize the balance of glossiness and impact resistance.
The matching of multistage particle sizes of the same rubber is difficult to realize, and the matching can be realized by compounding different types of rubbers, but the polymerization process is more complicated. The rubber with different particle diameters can also be compounded by using coupling agents with different functional groups, and the four-functional group coupling agent and the bifunctional group coupling agent are usually compounded; the metering accuracy and concentration of the coupling agent during compounding are difficult to ensure, and meanwhile, the reactivity of different coupling agents is inconsistent, so that the stability of the product is poor.
Therefore, there is still a need to develop a toughening agent suitable as an aromatic vinyl resin so that the aromatic vinyl resin achieves a balance of gloss and impact properties.
Disclosure of Invention
The invention aims to overcome the technical problem that the existing aromatic vinyl resin toughening agent is difficult to realize multistage particle size matching, and provides polybutadiene rubber and a preparation method thereof.
According to the first aspect of the present invention, there is provided a polybutadiene rubber containing a coupling center atom and having a molecular weight in a four-peak distribution, the number average molecular weight of the high molecular weight component being 280,000-470,000, the number average molecular weight of the second intermediate molecular weight component being 210,000-370,000, the number average molecular weight of the first intermediate molecular weight component being 150,000-250,000, the number average molecular weight of the low molecular weight component being 80,000-120,000, the content of the high molecular weight component being 1-30 wt%, the content of the second intermediate molecular weight component being 10-45 wt%, the content of the first intermediate molecular weight component being 20-40 wt%, and the content of the low molecular weight component being 5-55 wt%, based on the total amount of the polybutadiene rubber.
According to a second aspect of the present invention, there is provided a process for producing a polybutadiene rubber, which comprises the steps of:
(1) under the condition of anionic polymerization, 1, 3-butadiene is polymerized in an organic solvent in the presence of an organic lithium initiator and a structure regulator to obtain a polymerization solution containing polybutadiene, wherein the organic lithium initiator is used in an amount such that the number average molecular weight of the polybutadiene is 80,000-120,000;
(2) contacting the polymerization solution with a coupling agentCoupling reaction is carried out to obtain a coupling polymer solution, the coupling agent is one or more than two of four functional group coupling agents, and the molar weight of the coupling agent is nCThe molar weight of the organic lithium initiator is nI，2.8nI≥(nC×4)＞1.4nI。
According to a third aspect of the present invention, there is provided a polybutadiene rubber prepared by the preparation process described in the second aspect of the present invention.
According to a fourth aspect of the present invention, there is provided the use of a polybutadiene rubber according to the first or third aspect of the present invention as an aromatic vinyl resin toughening agent.
According to a fifth aspect of the present invention, there is provided an aromatic vinyl resin comprising an aromatic vinyl base resin and a toughening agent, wherein the toughening agent is the polybutadiene rubber of the first or third aspect of the present invention.
According to a sixth aspect of the present invention, there is provided a method for producing an aromatic vinyl resin, the method comprising: polymerizing an aromatic vinyl monomer in the presence of a toughening agent, wherein the toughening agent is the polybutadiene rubber of the first or third aspect of the present invention.
The polybutadiene rubber according to the present invention contains a coupling center atom and contains a high molecular weight component, a second intermediate molecular weight component, a first intermediate molecular weight component and a low molecular weight component, so that the particle size of the polybutadiene rubber is distributed in multiple stages, and when used as a toughening agent for aromatic vinyl resins, the components of each stage act synergistically with each other to give significantly improved impact resistance to the aromatic vinyl resins while maintaining high gloss of the aromatic vinyl resins.
According to the preparation method of the polybutadiene rubber, polybutadiene rubbers with different molecular weights are not required to be compounded, coupling agents with different functionalities are not required to be adopted, only the coupling agent with four functionalities is adopted, the coupling agent with four functionalities is excessive relative to an organic lithium initiator, and the polybutadiene rubber containing a high molecular weight component, a second intermediate molecular weight component, a first intermediate molecular weight component and a low molecular weight component can be obtained through one-step coupling reaction.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a polybutadiene rubber containing a coupling center atom and having a molecular weight in a four-peak distribution, the number average molecular weight (M) of the high molecular weight componentn) Is 280,000-470,000, preferably 300,000-450,000, more preferably 320,000-430,000; the number average molecular weight of the second intermediate molecular weight component is 210,000-370,000, preferably 230,000-360,000, more preferably 240,000-340,000; the number average molecular weight of the first intermediate molecular weight component is 150,000-250,000, preferably 160,000-240,000, more preferably 170,000-230,000; the number average molecular weight of the low molecular weight component is 80,000-120,000, preferably 85,000-115,000, more preferably 90,000-110,000. According to the polybutadiene rubber of the present invention, the number average molecular weight size relationship among the high molecular weight component, the second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component is as follows: the number average molecular weight of the high molecular weight component > the number average molecular weight of the second intermediate molecular weight component > the number average molecular weight of the first intermediate molecular weight component > the number average molecular weight of the low molecular weight component.
The polybutadiene rubber according to the present invention, the molecular weight distribution index (M) of the high molecular weight componentw/Mn) May be 1 to 1.1, preferably 1.02 to 1.08; the molecular weight distribution index of the second intermediate molecular weight component may be 1 to 1.1, preferably 1.02 to 1.08; the molecular weight distribution index of the first intermediate molecular weight component mayTo 1-1.1, preferably 1.02-1.08; the low molecular weight component may have a molecular weight distribution index of 1 to 1.1, preferably 1.02 to 1.08.
The polybutadiene rubber according to the present invention contains the high molecular weight component in an amount of 1 to 30% by weight, preferably 4 to 25% by weight, more preferably 8 to 22% by weight, based on the total amount of the polybutadiene rubber; the second intermediate molecular weight component is present in an amount of from 10 to 45 wt%, preferably from 12 to 42 wt%, more preferably from 25 to 40 wt%; the first intermediate molecular weight component is present in an amount of from 20 to 40 wt.%, preferably from 25 to 40 wt.%, more preferably from 26 to 38 wt.%; the content of the low molecular weight component is 5 to 55% by weight, preferably 8 to 40% by weight, more preferably 10 to 30% by weight.
The polybutadiene rubber according to the present invention may have a number average molecular weight of 150,000-250,000, preferably 170,000-240,000, more preferably 180,000-220,000. The polybutadiene rubber according to the present invention may have a molecular weight distribution index of 1.5 to 2.5, preferably 1.6 to 2.3. In the present invention, the number average molecular weight and the molecular weight distribution index of the polybutadiene rubber mean the overall number average molecular weight and the overall molecular weight distribution index of the polybutadiene rubber.
In the present invention, the number average molecular weight and the molecular weight distribution index are measured by gel permeation chromatography, and the mass percentage contents of the high molecular weight component, the second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component are measured by gel permeation chromatography. The gel permeation chromatography analysis adopts an HLC-8320 type gel permeation chromatograph of Tosoh corporation in Japan, chromatographic columns are TSKgel SuperMultiporeHZ-N and TSKgel SuperMultiporeHZ standard columns, a solvent is chromatographic pure Tetrahydrofuran (THF), narrow-distribution polystyrene is used as a standard sample, a polymer sample is prepared into a tetrahydrofuran solution with the mass concentration of 1mg/mL, the sample introduction amount is 10.00 mu L, the flow rate is 0.35mL/min, and the test temperature is 40.0 ℃. The calculation method of the mass percentage content of the high molecular weight component, the second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component comprises the following steps:
mass percent (%) of the high molecular weight component (peak area corresponding to the peak of the high molecular weight component/(peak area corresponding to the high molecular weight component + peak area corresponding to the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component + peak area corresponding to the low molecular weight component) in the GPC curve;
Mass percent (%) of the second intermediate molecular weight component being the peak area of the peak corresponding to the second intermediate molecular weight component in the GPC curve/(peak area corresponding to the high molecular weight component + peak area corresponding to the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component + peak area corresponding to the low molecular weight component);
mass percent (%) of the first intermediate molecular weight component (GPC curve) peak area corresponding to the peak of the first intermediate molecular weight component/(peak area corresponding to the high molecular weight component + peak area corresponding to the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component + peak area corresponding to the low molecular weight component);
the mass percentage (%) of the low-molecular weight component is the peak area of the peak corresponding to the low-molecular weight component in the GPC curve/(peak area corresponding to the high-molecular weight component + peak area corresponding to the second intermediate-molecular weight component + peak area corresponding to the first intermediate-molecular weight component + peak area corresponding to the low-molecular weight component).
In the present invention, the peak area of the peak of each component is a percentage of the peak area obtained by GPC measurement.
According to the polybutadiene rubber of the present invention, the viscosity of the polybutadiene rubber in a 5 wt% styrene solution at 25 ℃ may be 90cP or more, preferably 100-200cP, more preferably 120-180cP, and still more preferably 130-170 cP.
The polybutadiene rubber according to the present invention has a reduced 5 wt% styrene solution viscosity at 25 ℃ and thus has better processability, as compared to compounding a linear polybutadiene rubber having a component corresponding to the high molecular weight, a linear polybutadiene rubber having a component corresponding to the second intermediate molecular weight, a linear polybutadiene rubber having a component corresponding to the first intermediate molecular weight, and a linear polybutadiene rubber having a component corresponding to the low molecular weight. The polybutadiene rubber according to the present invention has a viscosity of X centipoise in a 5 wt% styrene solution at 25 ℃ and the low molecular weight component thereof has a viscosity of Y centipoise in a 5 wt% styrene solution at 25 ℃, and the ratio of X/Y may be 1 to 1.6, for example: 1. 1.1, 1.2, 1.3, 1.4, 1.5 or 1.6, preferably 1.2 to 1.5, more preferably 1.25 to 1.4. The compound obtained by compounding the linear polybutadiene rubber having a component corresponding to the high molecular weight, the linear polybutadiene rubber having a component corresponding to the second intermediate molecular weight, the linear polybutadiene rubber having a component corresponding to the first intermediate molecular weight, and the linear polybutadiene rubber having a component corresponding to the low molecular weight has a ratio of the viscosity to Y of usually 4 or more in a 5 wt% styrene solution at 25 ℃.
In the present invention, the viscosity of the rubber in a 5 wt% styrene solution at 25 ℃ is measured in accordance with the Q/SHYS.3155.SXJC06-2016 standard.
The polybutadiene rubber according to the present invention may have a Mooney viscosity at 100 ℃ of 70 to 80, preferably 45 to 75, more preferably 50 to 70, further preferably 55 to 60.
In the present invention, the Mooney viscosity is measured by a Mooney viscometer model SMV-201 SK-160 manufactured by Shimadzu corporation of Japan according to a method specified in the Chinese national standard GB/T1232-92, and the test conditions include: ML (1+4), test temperature 100 ℃.
The vinyl content of the polybutadiene rubber according to the present invention may be 8 to 20% by weight, preferably 10 to 16% by weight.
The polybutadiene rubber according to the present invention may have a cis 1, 4-structural unit content of 30 to 40% by weight.
In the present invention, vinyl means a structural unit in which 1, 3-butadiene is polymerized in a 1, 2-manner, and in the present invention, cis 1, 4-structural unit means a structural unit in which butadiene is polymerized in a 1, 4-manner and the configuration is cis. In the invention, the content of vinyl and the content of cis-1, 4-structural units are measured by a nuclear magnetic resonance spectroscopy, the solvent adopted in the test is deuterated chloroform, and tetramethylsilicon is used as an internal standard.
The polybutadiene rubber according to the present invention contains a coupling center atom. The coupling center atom may be derived from a coupling agent. Preferably, the coupling center atom is silicon and/or tin. According to the polybutadiene rubber of the present invention, the high molecular weight component, the second intermediate molecular weight component and the first intermediate molecular weight component contain a coupling center atom, and the low molecular weight component is substantially free of a coupled polymer and is a linear polymer. That is, according to the polybutadiene rubber of the present invention, the high molecular weight component, the second intermediate molecular weight component and the first intermediate molecular weight component are coupled polymers, which are components formed by reacting a coupling agent with the living terminal groups of the respective linear polymers to link at least two linear polymer chains together through the coupling center atom of the coupling agent.
The polybutadiene rubber according to the present invention may have a mass content of the coupling center atom of 85 to 230ppm, based on the total amount of the polybutadiene rubber, for example: 85. 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 149, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 194, 192, 193, 198, 195, 200, 196, 202, 209, 212, 204, 213, 204, 214. 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229 or 230ppm, preferably 105-190ppm, more preferably 110-180ppm, and even more preferably 115-175 ppm.
According to the polybutadiene rubber, the coupling agent is one or more than two of four-functional-group coupling agents. Specific examples of the coupling center atom of the coupling agent may include, but are not limited to, silicon and tin. Preferably, the coupling agent is tetrachlorosilane and/or tin tetrachloride.
According to the polybutadiene rubber of the present invention, in addition to the molecular chains of the high molecular weight component, the second intermediate molecular weight component and the first intermediate molecular weight component containing coupling center atoms, at least part of the molecular chains of the low molecular weight component also contain coupling center atoms, except that the coupling center atoms in the molecular chains of the low molecular weight component are connected to only one polymer chain. The polybutadiene rubber according to the present invention has a coupling center atom in the polybutadiene rubber in a molar percentage of NZThe molar percentage of the high molecular weight component is NHThe mole percentage of the second intermediate molecular weight component is NM1The mole percentage of the first intermediate molecular weight component is NM2The low molecular weight component is NLThe number of coupling arms of the high molecular weight component is AHAnd the number of coupling arms of the second intermediate molecular weight component is AM1The number of coupling arms of the first intermediate molecular weight component is A M2，4(NH+NM1+NM2+NL)≥(NZ×4)≥(NH×AH+NM1×AM1+NM2×AM2+NL)。(NZ×4)/(NH×AH+NM1×AM1+NM2×AM2+NL) Preferably 1 to 3, for example: 1. 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3, more preferably 1.3 to 2.8, and still more preferably 1.4 to 2.2.
In the present invention, the mass percentage of the coupling center atom is measured by a plasma method (ICP method), and the molar percentage of the coupling center atom is converted from this. In the invention, the mole percentage content and the coupling arm number of the high molecular weight component, the second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component are measured by adopting a GPC method, and the specific method comprises the following steps:
the number of coupling arms of the high molecular weight component is equal to the number average molecular weight of the high molecular weight component/the number average molecular weight of the low molecular weight component;
the number of coupling arms of the second intermediate molecular weight component ═ the number average molecular weight of the second intermediate molecular weight component/the number average molecular weight of the low molecular weight component;
the number of coupling arms of the first intermediate molecular weight component ═ the number average molecular weight of the first intermediate molecular weight component/the number average molecular weight of the low molecular weight component;
a mole percent of the high molecular weight component ═ (% peak area corresponding to the high molecular weight component/number average molecular weight of the high molecular weight component) ÷ (peak area corresponding to the high molecular weight component/number average molecular weight of the high molecular weight component + peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component + peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component);
A mole percent of the second intermediate molecular weight component ═ (% peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component) ÷ (peak area corresponding to the high molecular weight component/number average molecular weight of the high molecular weight component + peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component + peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component);
a mole percent of the first intermediate molecular weight component ═ a (peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component) ÷ (peak area corresponding to the high molecular weight component/number average molecular weight of the high molecular weight component + a peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component + a peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component + a peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component);
the mole percent of the low molecular weight component (peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component) ÷ (peak area corresponding to the high molecular weight component/number average molecular weight of the high molecular weight component + peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component + peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component).
The polybutadiene rubber according to the present invention may further contain at least one auxiliary agent to impart new properties to the polybutadiene rubber and/or to improve the properties of the polybutadiene rubber. The adjuvant may include an antioxidant. The type of the antioxidant is not particularly limited in the present invention and may be conventionally selected, and for example, the antioxidant may be a phenolic and/or amine antioxidant. Specifically, the antioxidant may be one or more of 4, 6-bis (octylthiomethyl) o-cresol (trade name: antioxidant 1520), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: antioxidant 1076), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (trade name: antioxidant 4020), N-cumyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010NA), and N-phenyl-2-naphthylamine (trade name: antioxidant D), and preferably, the antioxidant 1520 and the antioxidant 1076 are used. When the antioxidant 1520 and the antioxidant 1076 are used in combination, the weight ratio of the antioxidant 1520 to the antioxidant 1076 may be 1: 1-3. The antioxidant may be used in an amount conventionally used in the art. In one embodiment, the weight ratio of the antioxidant to the polybutadiene rubber may be 0.1 to 0.4: 100.
According to a second aspect of the present invention, there is provided a process for producing a polybutadiene rubber, which comprises the steps of:
(1) under the condition of anionic polymerization, 1, 3-butadiene is polymerized in an organic solvent in the presence of an organic lithium initiator and a structure regulator to obtain a polymerization solution containing polybutadiene, wherein the organic lithium initiator is used in an amount such that the number average molecular weight of the polybutadiene is 80,000-120,000;
(2) contacting the polymerization solution with a coupling agent to carry out coupling reaction to obtain a coupling polymer solution, wherein the coupling agent is one or more than two of four-functional group coupling agents, and the molar weight of the coupling agent is nCThe molar weight of the organic lithium initiator is nI，2.8nI≥(nC×4)＞1.4nI。
In the step (1), the organic lithium initiator can be various organic lithium compounds which are commonly used in the field of anionic polymerization and can initiate butadiene polymerization, and is preferably a compound shown as a formula I,
R1li (formula I)
In the formula I, R1Is C1-C6Alkyl of (C)3-C12Cycloalkyl of, C7-C14Aralkyl or C6-C12Aryl group of (1).
Said C is1-C6Alkyl of (2) includes C1-C6Straight chain alkyl of (2) and C3-C6Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl.
Said C is3-C12Specific examples of the cycloalkyl group of (a) may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
Said C is7-C14Specific examples of the aralkyl group of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl, phenyl-isopropyl, phenyl-n-pentyl and phenyl-n-butyl.
Said C is6-C12Specific examples of the aryl group of (a) may include, but are not limited to: phenyl, naphthyl, 4-methylphenyl and 4-ethylphenyl.
Specific examples of the organolithium initiator may include, but are not limited to: one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, cyclohexyllithium, phenyllithium, 2-naphthyllithium, 4-butylphenyl lithium, 4-methylphenyllithium and 4-butylcyclohexyllithium. Preferably, the organolithium initiator is n-butyllithium and/or sec-butyllithium. More preferably, the organolithium initiator is n-butyllithium.
In the step (1), the molecular weight of polybutadiene can be adjusted by adjusting the ratio of the organolithium initiator to 1, 3-butadiene. According to the preparation process of the present invention, in a preferred embodiment, in step (1), the organolithium initiator is used in an amount such that the polybutadiene has a number average molecular weight of 85,000-115,000, preferably 90,000-110,000. According to this preferred embodiment, the molar ratio of 1, 3-butadiene to the organolithium initiator may be 1400-: 1, preferably 1500-: 1, more preferably 1600-: 1. according to this preferred embodiment, the finally prepared polybutadiene rubber is suitable as a toughening agent for aromatic vinyl resins.
In the step (1), the structure regulator is used for regulating the vinyl content in the polybutadiene formed by polymerization, and may be one or more than two of an ether-type structure regulator and an amine-type structure regulator.
The ether type structure regulator can be one or more than two of aliphatic monoether, aliphatic polyether, aromatic ether and cyclic ether.
The aliphatic monoether can be one or more than two of aliphatic symmetrical monoethers and aliphatic asymmetrical monoethers. Specific examples of the aliphatic monoethers may include, but are not limited to: one or more of methyl ether, ethyl ether, propyl ether and methyl ethyl ether.
The aliphatic polyether can be one or more of aliphatic symmetrical polyether and aliphatic asymmetrical polyether. Specific examples of the aliphatic polyether may include, but are not limited to: one or more of ethylene glycol dialkyl ether, diethylene glycol dialkyl ether and diethylene glycol dialkyl ether. The alkyl group may be C1-C4Alkyl radicals, e.g. methyl, ethyl, n-propylIsopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
The aromatic ether may be anisole and/or diphenyl ether.
The cyclic ether may be one or more of tetrahydrofuran, tetrahydrofurfuryl alkyl ether and 1, 4-dioxan. Specific examples of the cyclic ether may include, but are not limited to: one or more than two of tetrahydrofuran, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl propyl ether, tetrahydrofurfuryl isopropyl ether, tetrahydrofurfuryl butyl ether and 1, 4-dioxycyclohexane.
The amine structure regulator can be one or more than two of N, N, N ', N' -tetramethyl ethylenediamine, N, N-dimethyl tetrahydrofurfuryl amine, triethylamine and tripropylamine.
In a preferred embodiment, the structure regulator in step (1) is one or more of tetrahydrofuran, tetrahydrofurfuryl alkyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether and diethylene glycol dialkyl ether, and the alkyl group may be C1-C4Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. In the preferred embodiment, the structure modifier is preferably one or more of tetrahydrofuran, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl propyl ether, tetrahydrofurfuryl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diethyl ether; more preferably one or more of tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether and tetrahydrofurfuryl propyl ether.
In step (1), the amount of the structure-regulating agent may be conventionally selected. In step (1), the molar ratio of the structure-regulating agent to the organolithium initiator may be 0.01 to 1: 1, preferably 0.02 to 0.8: 1, more preferably 0.04 to 0.7: 1.
In the step (1), the polymerization is carried out in an organic solvent, which may be any of various organic substances capable of mediating the polymerization reaction under solution polymerization conditions, preferably a nonpolar solvent, for example, a hydrocarbon solvent. The hydrocarbon solvent may be one or more selected from cyclohexane, n-hexane, n-pentane, n-heptane, isooctane, benzene and raffinate oil. The raffinate oil is the distillate oil left after the aromatic hydrocarbon is extracted from the catalytic reforming product rich in the aromatic hydrocarbon in the petroleum refining process. The solvent may be used in an amount conventional in the art. In general, in step (1), the solvent may be used in an amount such that the concentration of 1, 3-butadiene is 1 to 16% by weight, preferably 2 to 8% by weight.
In step (1), the polymerization may be carried out under conventional anionic polymerization conditions. The polymerization in the step (1) is carried out so that the conversion of 1, 3-butadiene is 99% by weight or more. Generally, in step (1), the polymerization may be carried out at a temperature of 0 to 100 ℃, preferably 40 to 95 ℃, more preferably 60 to 90 ℃. In step (1), the duration of the polymerization may be 20 to 80 minutes, preferably 30 to 60 minutes. In the step (1), the polymerization may be carried out at a pressure of 0.1 to 1MPa, preferably 0.2 to 0.5MPa, the pressure being a gauge pressure.
According to the preparation method of the invention, in the step (2), the coupling agent is used in excess, and the molar quantity of the organic lithium initiator is nI，2.8nI≥(nC×4)≥1.4nI. According to the preparation method, excessive coupling agents are adopted, the polybutadiene rubber with different molecular weights can be obtained through one-step coupling reaction, and more than two coupling agents are avoided or the polybutadiene rubber with different molecular weights is not compounded. Preferably, nC/nIThe ratio of (A) to (B) is 0.37-0.65: controlling the amount of the coupling agent and the organolithium initiator to be the ratio can further improve the performance of the finally prepared polybutadiene rubber as a toughening agent of the aromatic vinyl resin, so that the aromatic vinyl resin obtains better performance balance between the impact resistance and the optical performance. More preferably, nC/nIThe ratio of (A) to (B) is 0.37-0.5: 1. further preferably, nC/nIThe ratio of (A) to (B) is 0.4-0.45: 1.
in the step (2), the coupling agent is one or more than two of four-functional group coupling agents.
Preferably, the coupling agent is a silicon-containing coupling agent and/or a tin-containing coupling agent. More preferably, the coupling agent is tetrachlorosilane and/or tin tetrachloride.
In the step (2), the coupling reaction may be carried out at a temperature of 50 to 100 ℃, preferably 60 to 90 ℃, more preferably 70 to 80 ℃. The duration of the coupling reaction may be 20-40 minutes. The coupling reaction may be carried out at a pressure of from 0.1 to 1MPa, preferably from 0.2 to 0.5MPa, the pressure being gauge pressure.
In the step (2), the coupling agent is used in an amount such that the coupled polymer contains a high molecular weight component, a second intermediate molecular weight component, a first intermediate molecular weight component and a low molecular weight component, the number average molecular weight of the high molecular weight component is 280,000-470,000, preferably 300,000-450,000, more preferably 320,000-430,000; the number average molecular weight of the second intermediate molecular weight component is 210,000-370,000, preferably 230,000-360,000, more preferably 240,000-340,000; the number average molecular weight of the first intermediate molecular weight component is 150,000-250,000, preferably 160,000-240,000, more preferably 170,000-230,000; the number average molecular weight of the low molecular weight component is 80,000-120,000, preferably 85,000-115,000, more preferably 90,000-110,000; the content of the high molecular weight component is 1 to 30% by weight, preferably 4 to 25% by weight, more preferably 8 to 22% by weight, based on the total amount of the polybutadiene rubber; the second intermediate molecular weight component is present in an amount of from 10 to 45 wt%, preferably from 12 to 42 wt%, more preferably from 25 to 40 wt%; the first intermediate molecular weight component is present in an amount of from 20 to 40 wt.%, preferably from 25 to 40 wt.%, more preferably from 26 to 38 wt.%; the content of the low molecular weight component is 5 to 55% by weight, preferably 8 to 40% by weight, more preferably 10 to 30% by weight.
The preparation method according to the present invention preferably further comprises a step (3) of contacting the coupled polymer solution with a terminating agent to carry out a terminating reaction to obtain a terminated reaction solution.
The terminator may be any of various substances capable of terminating a living chain, which are commonly used in the field of anionic polymerization. The terminating agent may be C1-C4Preferably one or more of isopropyl alcohol, stearic acid, citric acid and carbon dioxide, more preferably carbon dioxide. The carbon dioxide is adopted for termination reaction, the carbon dioxide can form carbonate with metal ions (Li, Mg, Al, Fe and Zn) in a polymerization system to be separated from the polymer, the color development reaction of the metal ions is avoided, and the product has lower chroma. The carbon dioxide may be introduced into the reaction system in the form of a gas (for example, carbon dioxide gas having a gauge pressure of 0.2 to 1MPa, preferably 0.3 to 0.6 MPa) or may be introduced into the reaction system in the form of an aqueous dry ice solution (for example, having a concentration of 0.1 to 5% by weight).
The preparation method according to the present invention may further include step (4): adding at least one auxiliary agent to the terminated reaction liquid obtained in step (3) to impart new properties to the finally prepared polybutadiene rubber and/or to improve the properties of the finally prepared polybutadiene rubber.
In particular, the adjuvant may include an antioxidant. The type of the antioxidant is not particularly limited in the present invention and may be conventionally selected, and for example, the antioxidant may be a phenolic and/or amine antioxidant. Specifically, the antioxidant may be one or more of 4, 6-bis (octylthiomethyl) o-cresol (trade name: antioxidant 1520), N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name: antioxidant 1076), N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (trade name: antioxidant 4020), N-cumyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010NA), and N-phenyl-2-naphthylamine (trade name: antioxidant D), and is preferably one or more of antioxidant 1520 and antioxidant 1076. When the antioxidant 1520 and the antioxidant 1076 are used in combination, the weight ratio of the antioxidant 1520 to the antioxidant 1076 may be 1: 1-3. The antioxidant may be used in an amount conventionally used in the art. In one embodiment, the weight ratio of the antioxidant to 1, 3-butadiene may be from 0.1 to 0.4: 100.
according to the preparation method of the present invention, the obtained mixture can be purified and separated by a conventional method to obtain polybutadiene rubber. Specifically, the resulting mixture may be subjected to centrifugal separation, filtration, decantation, or hot water coagulation to obtain polybutadiene rubber; the resulting mixture may also be subjected to steam stripping to remove the solvent therefrom, thereby obtaining a polybutadiene rubber.
The polymerization method of the present invention may be carried out by a batch polymerization method or a continuous polymerization method, and is not particularly limited.
According to a third aspect of the present invention, there is provided a low-cis butadiene rubber prepared by the preparation method according to the second aspect of the present invention.
The polybutadiene rubber prepared by the method of the second aspect of the invention can be prepared into the molecular weight four-peak distribution polybutadiene rubber containing the high molecular weight component, the second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component without compounding by controlling the using amount of the coupling agent to be excessive.
According to a fourth aspect of the present invention, there is provided the use of a polybutadiene rubber according to the first or third aspect of the present invention as an aromatic vinyl resin toughening agent.
The polybutadiene rubber according to the present invention may be added to the aromatic vinyl resin as a toughening agent by a conventional method, for example: the polybutadiene rubber may be added during polymerization to form the aromatic vinyl resin, or may be added to the aromatic vinyl resin as a toughening agent.
According to a fifth aspect of the present invention, there is provided an aromatic vinyl resin comprising an aromatic vinyl base resin and a toughening agent, wherein the toughening agent is the polybutadiene rubber of the first or third aspect of the present invention.
The aromatic vinyl base matrix resin may be a polymer formed by homopolymerizing or copolymerizing an aromatic vinyl monomer, which means a monomer having both an aromatic group (e.g., phenyl group) and a vinyl group in a molecular structure. Specific examples of the aromatic vinyl monomer may include, but are not limited to: one or the combination of more than two of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and vinylnaphthalene. Preferably, the aromatic vinyl monomer is styrene.
One preferred example of the aromatic vinyl resin is high impact polystyrene.
The amount of polybutadiene rubber used as the toughening agent may be conventionally selected. Specifically, the polybutadiene rubber may be used in an amount of 5 to 15 parts by weight, preferably 6 to 12 parts by weight, relative to 100 parts by weight of the high impact polystyrene.
According to a sixth aspect of the present invention, there is provided a method for producing an aromatic vinyl resin, the method comprising: polymerizing an aromatic vinyl monomer in the presence of a toughening agent, wherein the toughening agent is the polybutadiene rubber of the first or third aspect of the present invention.
According to the method for preparing the aromatic vinyl resin of the present invention, specific examples of the aromatic vinyl monomer may include, but are not limited to: one or the combination of more than two of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and vinylnaphthalene. Preferably, the aromatic vinyl monomer is styrene.
According to the method for preparing an aromatic vinyl resin of the present invention, the polymerization reaction may be carried out by a radical polymerization method. The type of the radical initiator used in the radical polymerization is not particularly limited, and may be selected conventionally, and may be one or two or more kinds of thermal decomposition type radical initiators, for example. Preferably, the radical initiator is one or more than two of a peroxide type initiator and an azobisnitrile type initiator. Specific examples of the radical initiator may include, but are not limited to: one or more of diacyl peroxide, peroxy-2-ethylhexyl tert-butyl carbonate, peroxydicarbonate, peroxycarboxylate, alkyl peroxide and azobisnitrile compounds (such as azobisisobutyronitrile and azobisisoheptonitrile). Preferably, the free radical initiator is one or more than two of dibenzoyl peroxide, di-o-methylbenzoyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexylcarbonate.
The amount of the radical initiator to be used may be conventionally selected so as to be able to obtain an aromatic vinyl resin having a desired molecular weight. Methods for determining the amount of initiator to be used based on the molecular weight of the polymer to be expected are well known to those skilled in the art and will not be described in detail herein.
According to the method for preparing an aromatic vinyl resin of the present invention, the polymerization reaction can be carried out under conventional conditions. Generally, the conditions of the polymerization reaction include: the temperature is 100 ℃ and 170 ℃ and the time is 4-12 hours (for example, 7-9 hours). Preferably, the polymerization reaction can be carried out in stages at different temperatures. For example: the polymerization reaction may include a first polymerization reaction, a second polymerization reaction, a third polymerization reaction, and a fourth polymerization reaction, the first polymerization reaction may be performed at a temperature of 115-125 ℃, and the duration of the first polymerization reaction may be 3-4 hours; the second polymerization reaction may be performed at a temperature of 130-140 ℃, and the duration of the second polymerization reaction may be 1-3 hours; the third polymerization reaction may be carried out at a temperature of 150-160 ℃, and the duration of the third polymerization reaction may be 0.5-1.5 hours; the fourth polymerization reaction may be carried out at a temperature of 165-175 deg.C, and the duration of the fourth polymerization reaction may be 0.5-1.5 hours.
The high impact polystyrene has excellent impact resistance, and the cantilever beam impact strength of the high impact polystyrene can be 16kJ/m2Above (e.g. 16-25 kJ/m)2) Typically 17kJ/m2Above, e.g. 18-22kJ/m2(ii) a The 60 ℃ surface gloss may be 55 or more, typically 60 or more, for example 65 to 75.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, the monomer conversion was determined gravimetrically as the weight percent of polymer weight after solvent removal as a function of monomer charge.
In the following examples and comparative examples, the content of 1, 2-polymerized structural units in the polybutadiene rubber was a vinyl content, measured by AVANCEDRX400MHz type nuclear magnetic resonance apparatus manufactured by BRUKER, at a frequency of 400MHz, with deuterated chloroform as the solvent, and tetramethylsilane as the internal standard. The gel permeation chromatography analysis was performed on a gel permeation chromatograph model HLC-8320 from the company eastern cao, japan, wherein the test conditions included: the chromatographic column is TSKgel SuperMultiporeHZ-N, the standard column is TSKgel SuperMultiporeHZ, the solvent is chromatographically pure THF, the calibration standard sample is polystyrene, the sample mass concentration is 1mg/mL, the sample amount is 10.00 mu L, the flow rate is 0.35mL/min, and the test temperature is 40 ℃. Plasma analysis (ICP) was carried out on an ICPMS-2030, model number available from Shimadzu, Japan, and was determined according to the GB/T18174-2000 standard.
In the following examples and comparative examples, the viscosity of a 5 wt% styrene solution of rubber at a temperature of 25 ℃ was measured at a constant temperature of 25 ℃ using a capillary viscometer.
In the following examples and comparative examples, the Mooney viscosity was measured using a Mooney viscometer without a rotor, model SMV-201SK-160, manufactured by Shimadzu corporation of Japan, in which the preheating time was 1min, the rotation time was 4min, and the measuring temperature was 100 ℃.
In the following examples and comparative examples, the color was determined according to the Q/SH 3165251-: the color system is CIELAB, the optical geometry is 45/0, the light source is a C light source, the observation angle is 2 degrees, and the diameter of the observation hole is 30 mm.
In the following examples and comparative examples, mechanical properties were measured using an INSTRON 5567 Universal Material testing machine, UK, in which notched Izod impact Strength was measured according to GB/T1843-1996 (kJ/m)2). In the following examples and comparative examples, 60 ℃ gloss was measured according to ASTM D526(60 ℃).
In the following examples and comparative examples, the pressure refers to gauge pressure.
In the following examples and comparative examples, antioxidant 1520 was purchased from national pharmaceutical Agents; antioxidant 1076 was obtained from Inokay reagent, tetrahydrofurfurylether from carbofuran reagent, silicon tetrachloride and methyltrichlorosilane from carbofuran reagent (analytically pure, diluted to a concentration of 0.1mol/L), and n-butyllithium and sec-butyllithium from carbofuran reagent, each diluted with hexane to a concentration of 0.4 mol/L.
Examples 1-9 serve to illustrate the invention.
Example 1
(1) Under the protection of nitrogen, adding an organic solvent, 1, 3-butadiene and a structure regulator into a polymerization reaction kettle, raising the temperature in the polymerization reaction kettle to the polymerization reaction temperature, then adding an organic lithium initiator, and carrying out anionic solution polymerization reaction at the temperature (the temperature, the pressure and the time of the polymerization reaction are shown in table 1) to obtain a polymerization reaction mixed solution.
(2) An excess amount of a tetrafunctional coupling agent (specific kind and amount are shown in Table 2) was added to the polymerization mixture, and a coupling reaction was carried out under the conditions shown in Table 2 (coupling reaction temperature, pressure and time are shown in Table 2) to obtain a coupling reaction mixture.
(3) After the coupling reaction was completed, a terminator (specific type and amount shown in table 2) was added to the coupling reaction mixture to terminate the coupling reaction. To the mixture obtained by the termination reaction, an antioxidant (the kind and amount thereof are shown in Table 2) was added and mixed to obtain a polymerization solution of polybutadiene rubber. The resulting polymerization solution was subjected to steam coagulation desolventization treatment and dried to obtain polybutadiene rubbers, the structure and property parameters of which are listed in tables 3 and 4.
Examples 2 to 9
Polybutadiene rubbers were prepared by the same procedures as in example 1, except that the conditions shown in tables 1 and 2 were respectively employed to obtain polybutadiene rubbers, the structure and property parameters of which are shown in tables 3 and 4.
Comparative example 1
Polybutadiene rubbers were prepared by the same procedures as in example 1, except that in the step (2), the amount of the coupling agent was as shown in Table 2, and the structural and property parameters of the resulting polybutadiene rubbers were as shown in tables 3 and 4.
Comparative example 2
Polybutadiene rubbers were prepared by the same procedures as in example 1, except that in the step (2), the amount of the coupling agent was as shown in Table 2, and the structural and property parameters of the resulting polybutadiene rubbers were as shown in tables 3 and 4.
Comparative example 3
Polybutadiene rubber was prepared by the same method as in example 1, except that in step (2), silicon tetrachloride as a coupling agent was replaced with an equimolar amount of methyltrichlorosilane. The structural and property parameters of the polybutadiene rubber obtained are listed in tables 3 and 4.
Comparative example 4
Polybutadiene rubber was prepared by the same method as in example 1, except that the amount of n-butyllithium used as the initiator in step (1) was 8mmol, and the amount of tetrachlorosilane used in step (2) was 3.4 mmol. The structural and property parameters of the polybutadiene rubber obtained are listed in tables 3 and 4.
Comparative example 5
Low-cis polybutadiene linear polymers having number average molecular weights of 9.2 ten thousand, 18.5 ten thousand, 26.2 ten thousand and 35.4 ten thousand were prepared in the same manner as in steps (1) and (3) of example 1, respectively (see table 1 and table 3 for specific reaction conditions), and the four linear polymers were mixed in a mass ratio of 9.2 ten thousand/18.5 ten thousand/26.2 ten thousand/35.4 ten thousand-0.98/2.1/2.28/1 to obtain polybutadiene rubber linear copolymers, the structure and property parameters of which are listed in tables 3 and 4.
TABLE 1
Figure BDA0002067355160000201
Figure BDA0002067355160000211
TABLE 2
Figure BDA0002067355160000212
TABLE 3
Figure BDA0002067355160000221
1: the sum of the areas of the peak corresponding to the high molecular weight component (i.e., the first peak), the peak corresponding to the second intermediate molecular weight component (i.e., the second peak), the first intermediate molecular weight component (i.e., the third peak), and the peak corresponding to the low molecular weight component (i.e., the fourth peak) in the GPC curve is taken as a reference.
TABLE 4
Figure BDA0002067355160000222
1: X/Y, X being the viscosity of the polybutadiene rubber prepared in this example or comparative example in a 5 wt.% styrene solution at 25 ℃ and Y being the viscosity of the low molecular weight component of the polybutadiene rubber prepared in this example or comparative example in a 5 wt.% styrene solution at 25 ℃.
2: the measurement was carried out by a plasma method.
3：AHNumber average molecular weight of the high molecular weight component/number average molecular weight of the low molecular weight component;
AM1Number average molecular weight of the second intermediate molecular weight component/number average molecular weight of the low molecular weight component;
AM2number average molecular weight of the first intermediate molecular weight component/number average molecular weight of the low molecular weight component;
NH(peak area corresponding to high molecular weight component/number average molecular weight of high molecular weight component) ÷ (peak area corresponding to high molecular weight component/number average molecular weight of high molecular weight component + peak area corresponding to second intermediate molecular weight component/number average molecular weight of second intermediate molecular weight component + peak area corresponding to first intermediate molecular weight component/number average molecular weight of first intermediate molecular weight component + peak area corresponding to low molecular weight component/number average molecular weight of low molecular weight component);
NM1(peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component) ÷ (peak area corresponding to the high molecular weight component/number average molecular weight of the high molecular weight component + peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component + peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component);
NM2(peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component) ÷ (peak area corresponding to the high molecular weight component/number average molecular weight of the high molecular weight component + peak area corresponding to the second intermediate molecular weight component/number average molecular weight of the second intermediate molecular weight component + peak area corresponding to the first intermediate molecular weight component/number average molecular weight of the first intermediate molecular weight component + peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component);
NL(peak area corresponding to low molecular weight component/number average molecular weight of low molecular weight component) ÷ (peak area corresponding to high molecular weight component/number average molecular weight of high molecular weight component + peak area corresponding to second intermediate molecular weight component/number average molecular weight of second intermediate molecular weight component + peak area corresponding to first intermediate molecular weight component/number average molecular weight of first intermediate molecular weight component + peak area corresponding to low molecular weight component/number average molecular weight of low molecular weight component).
As can be seen from Table 4, the polybutadiene rubber according to the present invention has a content of 4 times the number of coupling center atoms in combination with (N)H×AH+NM1×AM1+NM2×AM2+NL) The ratio of (A) to (B) is more than 1, which indicates that most molecular chains contain coupling center atoms in the polybutadiene rubber, i.e., not only the molecular chains of the high molecular weight component, the second intermediate molecular weight component and the first intermediate molecular weight component formed by coupling contain coupling center atoms, but also the molecular chain of the low molecular weight component basically contains coupling center atoms. Example 1 was compared to comparative example 5 It can be seen that the low cis polybutadiene rubber according to the present invention has a reduced viscosity and thus, better processability, compared to a mixture obtained by mixing four linear polymers. It can also be seen from Table 4 that the polybutadiene rubber according to the present invention has a low color and is suitable for use as a toughening agent for aromatic vinyl resins.
Experimental examples 1 to 9
Experimental examples 1-9 high impact polystyrene resin was prepared by a conventional bulk method using the polybutadiene rubbers prepared in examples 1-9 as toughening agents, respectively, the proportion of the toughening agent to styrene monomer was 8%, and high impact polystyrene was obtained by a specific polymerization method:
mixing a toughening agent, styrene and a free radical initiator, carrying out polymerization with stirring, carrying out vacuum flash evaporation on a reaction product after the polymerization reaction is finished, removing unreacted monomers and a solvent to obtain the high impact polystyrene, wherein the polymerization reaction conditions are listed in Table 5, and the performance parameters of the prepared high impact polystyrene are listed in Table 6.
Experimental comparative examples 1 to 5
High impact polystyrene was prepared in the same manner as in experimental example 1, except that the low cis-polybutadiene prepared in comparative examples 1 to 5 was used as the toughening agent, respectively. The polymerization conditions are listed in Table 5 and the properties of the high impact polystyrene prepared are listed in Table 6.
Experimental comparative examples 6 to 7
High impact polystyrene was prepared in the same manner as in experimental example 1, except that Japanese Asahi chemical-formed products 720A and 730A (solvent-removed) were used as the toughening agent, respectively. The polymerization conditions are listed in Table 5 and the properties of the high impact polystyrene prepared are listed in Table 6.
Reference Experimental example 1
High impact polystyrene was prepared in the same manner as in experimental example 1, except that a toughening agent was not used. The performance parameters of the polymers prepared are listed in table 6.
TABLE 5
Figure BDA0002067355160000241
TABLE 6
Numbering Notched Izod impact Strength (kJ/m)2) Surface gloss (60o)
Experimental example 1 19.8 72
Experimental example 2 20.8 66
Experimental example 3 20.4 70
Experimental example 4 20.6 69
Experimental example 5 19.5 69
Experimental example 6 18.6 70
Experimental example 7 19.3 62
Experimental example 8 17.1 65
Experimental example 9 17.6 57
Experimental comparative example 1 15.6 58
Experimental comparative example 2 7.8 65
Experimental comparative example 3 13.8 64
Experimental comparative example 4 12.6 73
Experimental comparative example 5 17.4 34
Experimental comparative example 6 7.9 79
Experimental comparative example 7 10.8 74
Experimental reference example 1 1.2 94
As can be seen from the results in Table 6, the high impact polystyrene prepared using the polybutadiene rubber of the present invention as a toughening agent has significantly improved impact resistance while maintaining good gloss.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (23)

1. A polybutadiene rubber contains a coupling center atom, the molecular weight of the polybutadiene rubber is in a four-peak distribution, the number average molecular weight of a high molecular weight component is 280,000-470,000, the number average molecular weight of a second intermediate molecular weight component is 210,000-370,000, the number average molecular weight of a first intermediate molecular weight component is 150,000-250,000, the number average molecular weight of a low molecular weight component is 80,000-120,000, and based on the total amount of the polybutadiene rubber, the content of the high molecular weight component is 1-30 wt%, the content of the second intermediate molecular weight component is 10-45 wt%, the content of the first intermediate molecular weight component is 20-40 wt%, and the content of the low molecular weight component is 5-55 wt%.
2. The polybutadiene rubber according to claim 1, wherein the number average molecular weight of said high molecular weight component is 300,000-450,000, preferably 320,000-430,000; the number average molecular weight of the second intermediate molecular weight component is 230,000-360,000, preferably 240,000-340,000; the number average molecular weight of the first intermediate molecular weight component is 160,000-240,000, preferably 170,000-230,000; the number average molecular weight of the low molecular weight component is 85,000-115,000, preferably 90,000-110,000;
Preferably, the molecular weight distribution index of the high molecular weight component is 1 to 1.1, the molecular weight distribution index of the second intermediate molecular weight component is 1 to 1.1, the molecular weight distribution index of the first intermediate molecular weight component is 1 to 1.1, and the molecular weight distribution index of the low molecular weight component is 1 to 1.1.
3. The polybutadiene rubber according to claim 1 or 2, wherein the content of said high molecular weight component is 4-25 wt.%, preferably 8-22 wt.%, based on the total amount of the polybutadiene rubber; the second intermediate molecular weight component is present in an amount of 12 to 42 wt.%, preferably 25 to 40 wt.%; the content of the first intermediate molecular weight component is 25 to 40% by weight, preferably 26 to 38% by weight; the content of the low molecular weight component is 8 to 40% by weight, preferably 10 to 30% by weight.
4. The polybutadiene rubber according to any one of claims 1-3, wherein the polybutadiene rubber has a number average molecular weight of 150,000-250,000, preferably 170,000-240,000, more preferably 180,000-220,000;
preferably, the polybutadiene rubber has a molecular weight distribution index of 1.5 to 2.5.
5. The polybutadiene rubber according to any one of claims 1-4, wherein the polybutadiene rubber has a viscosity of 90cP or more, preferably 100-200cP, more preferably 120-180cP, in a 5 wt% styrene solution at 25 ℃;
Preferably, the polybutadiene rubber has a viscosity of X centipoise in a 5 wt% styrene solution at 25 ℃, the low molecular weight component of the polybutadiene rubber has a viscosity of Y centipoise in a 5 wt% styrene solution at 25 ℃, and the ratio of X/Y is 1 to 1.6, preferably 1.2 to 1.5.
6. The polybutadiene rubber according to any one of claims 1-5, wherein the Mooney viscosity at 100 ℃ of the polybutadiene rubber is from 70 to 80, preferably from 45 to 75, more preferably from 50 to 70.
7. The polybutadiene rubber according to any one of claims 1-6, wherein the vinyl content of the polybutadiene rubber is 8-20 wt.%, preferably 10-16 wt.%.
8. The polybutadiene rubber according to any one of claims 1 to 7, wherein the polybutadiene rubber has a cis 1, 4-structural unit content of 30 to 40% by weight.
9. The polybutadiene rubber of any one of claims 1-8, wherein said high molecular weight component, said second intermediate molecular weight component and said first intermediate molecular weight component contain coupling center atoms, at least a portion of said low molecular weight component contains coupling center atoms, said low molecular weight component being a linear polymer;
Preferably, the coupling center atom is silicon and/or tin;
more preferably, the mass content of the coupling center atom is 85 to 230ppm, preferably 100-200ppm, more preferably 105-190ppm, based on the total amount of the low-cis polybutadiene rubber.
10. The polybutadiene rubber of claim 9, wherein the coupling center atom is derived from a coupling agent;
preferably, the coupling agent is one or more than two of four-functional group coupling agents;
more preferably, the coupling agent is tetrachlorosilane and/or tin tetrachloride.
11. According to claim 10The polybutadiene rubber, wherein the polybutadiene rubber contains a coupling center atom in a molar percentage of NZThe molar percentage of the high molecular weight component is NHThe mole percentage of the second intermediate molecular weight component is NM1The mole percentage of the first intermediate molecular weight component is NM2The low molecular weight component is NLThe number of coupling arms of the high molecular weight component is AHAnd the number of coupling arms of the second intermediate molecular weight component is AM1The number of coupling arms of the first intermediate molecular weight component is AM2，4(NH+NM1+NM2+NL)≥(NZ×4)≥(NH×AH+NM1×AM1+NM2×AM2+NL)；
Preferably, (N)Z×4)/(NH×AH+NM1×AM1+NM2×AM2+NL) The ratio of (A) to (B) is 1-3;
more preferably, (N)Z×4)/(NH×AH+NM1×AM1+NM2×AM2+NL) The ratio of (A) to (B) is 1.3-2.8;
More preferably, (N)Z×4)/(NH×AH+NM1×AM1+NM2×AM2+NL) The ratio of (A) to (B) is 1.4-2.2.
12. A method for preparing polybutadiene rubber, which comprises the following steps:
(1) under the condition of anionic polymerization, 1, 3-butadiene is polymerized in an organic solvent in the presence of an organic lithium initiator and a structure regulator to obtain a polymerization solution containing polybutadiene, wherein the organic lithium initiator is used in an amount such that the number average molecular weight of the polybutadiene is 80,000-120,000;
(2) contacting the polymerization solution with a coupling agent to carry out coupling reaction to obtain a coupling polymer solution, wherein the coupling agent is one or more than two of four-functional group coupling agents, and the molar weight of the coupling agent is nCThe organic lithium initiatorThe molar weight of the hair agent is nI，2.8nI≥(nC×4)≥1.4nI。
13. The production method according to claim 12, wherein, in the step (2), n isC/nIThe ratio of (A) to (B) is 0.37-0.65: 1, preferably 0.37 to 0.5: 1, more preferably 0.4 to 0.45: 1;
preferably, in step (2), the coupling agent is used in an amount such that the coupled polymer contains a high molecular weight component having a number average molecular weight of 280,000-470,000, preferably 300,000-450,000, more preferably 320,000-430,000, a second intermediate molecular weight component, a first intermediate molecular weight component and a low molecular weight component; the number average molecular weight of the second intermediate molecular weight component is 210,000-370,000, preferably 230,000-360,000, more preferably 240,000-340,000; the number average molecular weight of the first intermediate molecular weight component is 150,000-250,000, preferably 160,000-240,000, more preferably 170,000-230,000; the number average molecular weight of the low molecular weight component is 80,000-120,000, preferably 85,000-115,000, more preferably 90,000-110,000; the content of the high molecular weight component is 1 to 30% by weight, preferably 4 to 25% by weight, more preferably 8 to 22% by weight, based on the total amount of the polybutadiene rubber; the second intermediate molecular weight component is present in an amount of from 10 to 45 wt%, preferably from 12 to 42 wt%, more preferably from 25 to 40 wt%; the first intermediate molecular weight component is present in an amount of from 20 to 40 wt.%, preferably from 25 to 40 wt.%, more preferably from 26 to 38 wt.%; the content of the low molecular weight component is 5 to 55% by weight, preferably 8 to 40% by weight, more preferably 10 to 30% by weight.
14. The production method according to claim 12 or 13, wherein, in the step (2), the coupling reaction is carried out at a temperature of 50 to 100 ℃, the duration of the coupling reaction is 20 to 40 minutes, the coupling reaction is carried out at a pressure of 0.1 to 1MPa, and the pressure is a gauge pressure.
15. The production method according to any one of claims 12 to 14, wherein the coupling agent is one or two or more of tetrafunctional coupling agents;
preferably, the coupling agent is a silicon-containing coupling agent and/or a tin-containing coupling agent;
more preferably, the coupling agent is tetrachlorosilane and/or tin tetrachloride.
16. The production method according to any one of claims 12 to 15, wherein the organolithium initiator is a compound represented by formula I,
R1li (formula I)
In the formula I, R1Is C1-C6Alkyl of (C)3-C12Cycloalkyl of, C7-C14Aralkyl or C6-C12Aryl of (a);
preferably, the organolithium initiator is one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, cyclohexyllithium, phenyllithium, 2-naphthyllithium, 4-butylphenyl lithium, 4-methylphenyl lithium and 4-butylcyclohexyllithium;
Preferably, in step (1), the organolithium initiator is used in an amount such that the polybutadiene has a number average molecular weight of 85,000-115,000, preferably 90,000-110,000;
preferably, in the step (1), the molar ratio of the 1, 3-butadiene to the organic lithium initiator is 1400-: 1, preferably 1500-: 1, more preferably 1600-: 1.
17. the production method according to any one of claims 12 to 16, wherein the structure-regulating agent is one or more of an ether-type structure-regulating agent and an amine-type structure-regulating agent;
preferably, the structure regulator is one or more of tetrahydrofuran, tetrahydrofurfuryl alkyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether and diethylene glycol dialkyl ether, and the alkyl is preferably C1-C4An alkyl group;
more preferably, the structure regulator is one or more of tetrahydrofuran, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl propyl ether, tetrahydrofurfuryl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol diethyl ether;
further preferably, the structure regulator is one or more than two of tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether and tetrahydrofurfuryl propyl ether;
Preferably, in step (1), the molar ratio of the structure modifier to the organolithium initiator is from 0.01 to 1: 1.
18. the production method according to any one of claims 12 to 17, wherein, in the step (1), the polymerization is carried out at a temperature of 0 to 100 ℃, preferably 40 to 90 ℃, the duration of the polymerization is 20 to 80 minutes, preferably 30 to 60 minutes, the polymerization is carried out at a pressure of 0.1 to 1MPa, preferably 0.2 to 0.5MPa, and the pressure is a gauge pressure.
19. The production method according to any one of claims 12 to 18, further comprising a step (3) of contacting the coupled polymer solution with a terminating agent to carry out a termination reaction;
preferably, the terminating agent is C1-C4Preferably, the alcohol, organic acid and carbon dioxide are one or more selected from isopropanol, stearic acid, citric acid and carbon dioxide.
20. A polybutadiene rubber prepared by the preparation process as set forth in claim 19.
21. Use of the polybutadiene rubber as described in any one of claims 1-11 and 20, as a toughening agent for aromatic vinyl resins.
22. An aromatic vinyl resin comprising an aromatic vinyl base resin and a toughening agent, wherein the toughening agent is the polybutadiene rubber according to any one of claims 1 to 11 and 20.
23. A method for preparing an aromatic vinyl resin, comprising: polymerizing an aromatic vinyl monomer in the presence of a toughening agent, wherein the toughening agent is the polybutadiene rubber of any one of claims 1-11 and 20.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251264A (en) * 2017-07-14 2019-01-22 中国石油化工股份有限公司 Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof
CN109251262A (en) * 2017-07-14 2019-01-22 中国石油化工股份有限公司 Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof
JP2019052284A (en) * 2017-09-13 2019-04-04 中国石油化工股▲ふん▼有限公司 Low cis-polybutadiene rubber, composition and aromatic vinyl resin, and method for preparing them

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251264A (en) * 2017-07-14 2019-01-22 中国石油化工股份有限公司 Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof
CN109251262A (en) * 2017-07-14 2019-01-22 中国石油化工股份有限公司 Low cis polybutadiene rubber and preparation method thereof and HIPS resin and preparation method thereof
JP2019052284A (en) * 2017-09-13 2019-04-04 中国石油化工股▲ふん▼有限公司 Low cis-polybutadiene rubber, composition and aromatic vinyl resin, and method for preparing them

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