CN111978445B - Low cis-polybutadiene rubber, preparation method and application thereof, and aromatic vinyl resin and preparation method - Google Patents

Low cis-polybutadiene rubber, preparation method and application thereof, and aromatic vinyl resin and preparation method Download PDF

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CN111978445B
CN111978445B CN201910425474.3A CN201910425474A CN111978445B CN 111978445 B CN111978445 B CN 111978445B CN 201910425474 A CN201910425474 A CN 201910425474A CN 111978445 B CN111978445 B CN 111978445B
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molecular weight
polybutadiene rubber
low cis
weight component
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CN111978445A (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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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a low cis-polybutadiene rubber and a preparation method thereof, and an aromatic vinyl resin using the rubber as a toughening agent and a preparation method thereof. The preparation method of the low cis-polybutadiene rubber comprises the steps of polymerizing 1, 3-butadiene in an organic solvent in the presence of an organolithium initiator and a structure regulator, and contacting the obtained polymerization solution with a coupling agent for coupling reaction, wherein the coupling agent is a trifunctional coupling agent, and the molar quantity of the coupling agent is n C The molar amount of the organolithium initiator is n I ，(2.1×n I )≥(n C ×3)＞n I . The preparation method obtains the low cis-polybutadiene rubber containing a high molecular weight component, a medium molecular weight component and a low molecular weight component through one-step coupling reaction, and the low cis-polybutadiene rubber is used as a toughening agent of an aromatic vinyl resin to enable the aromatic vinyl resin to have improved impact resistance and good glossiness.

Description

Low cis-polybutadiene rubber, preparation method and application thereof, and aromatic vinyl resin and preparation method
Technical Field
The invention relates to low cis-polybutadiene rubber and a preparation method and application thereof, and also relates to aromatic vinyl resin using the low cis-polybutadiene rubber as a toughening agent and a preparation method thereof.
Background
Conventional aromatic vinyl resins such as: in the preparation of high impact polystyrene resins (HIPS resins), the rubber conventionally selected for use as the toughening agent may be a low cis-polybutadiene rubber, a high cis-polybutadiene rubber, a butadiene-isoprene copolymer, a solution polymerized styrene-butadiene rubber, a styrene-butadiene-styrene copolymer, and particularly preferably a low cis-polybutadiene rubber and a high cis-polybutadiene rubber. For low temperature toughness resins, low cis polybutadiene rubber is generally selected for toughening.
The molecular weight and the distribution of the toughening rubber have obvious influence on the impact resistance of the HIPS resin with a continuous body, and the molecular weight of the toughening rubber is usually too small, so that the toughening effect is poor; the rubber particle size is too concentrated, and the glossiness and impact resistance of the resin are poor. In the selection of the toughening agent, rubber with different particle sizes needs to be matched so as to realize the synergistic effect of the rubber with different particle sizes and realize the balance of glossiness and impact resistance.
The same rubber is difficult to realize the matching of the multi-level particle sizes, and can be realized by adopting different rubber compounding, but the polymerization process is more complex. Rubber with different particle sizes can also be realized by compounding by using coupling agents with different functional groups, and the four-functional group coupling agent and the two-functional group coupling agent are generally adopted for compounding; the accuracy and concentration of metering are difficult to ensure when the coupling agents are compounded, and meanwhile, the reactivity of different coupling agents is inconsistent, so that the stability of the product is poor.
Accordingly, there remains a need to develop tougheners suitable as aromatic vinyl resins such that the aromatic vinyl resins achieve a balance of gloss and impact properties.
Disclosure of Invention
The invention aims to solve the technical problem that the existing aromatic vinyl resin toughening agent is difficult to realize multi-stage particle size matching, and provides a low-cis-polybutadiene rubber and a preparation method thereof.
According to a first aspect of the present invention, there is provided a low cis-polybutadiene rubber comprising a coupling center atom, a high molecular weight component having a number average molecular weight of 210,000-360,000, a medium molecular weight component having a number average molecular weight of 150,000-250,000, and a low molecular weight component having a number average molecular weight of 80,000 to 120,000, wherein the high molecular weight component is present in an amount of 4 to 55 wt%, the medium molecular weight component is present in an amount of 25 to 50 wt%, and the low molecular weight component is present in an amount of 5 to 70 wt%, based on the total amount of the low cis-polybutadiene rubber.
According to a second aspect of the present invention, there is provided a process for producing a low cis-polybutadiene rubber, comprising the steps of:
(1) Polymerizing 1, 3-butadiene in an organic solvent in the presence of an organolithium initiator and a structure regulator under anionic polymerization conditions to obtain a polymerization solution containing polybutadiene;
(2) The polymerization solution is contacted with a coupling agent for coupling reaction to obtain a coupled polymer solution, the coupling agent is one or more than two of trifunctional coupling agents, and the molar weight of the coupling agent is n C The molar amount of the organolithium initiator is n I ，(2.1×n I )≥(n C ×3)＞n I 。
According to a third aspect of the present invention, there is provided a low cis-polybutadiene rubber produced by the production method according to the second aspect of the present invention.
According to a fourth aspect of the present invention there is provided the use of a low cis 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 low cis polybutadiene rubber according to 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 low cis polybutadiene rubber according to the first or third aspect of the present invention.
The low cis-polybutadiene rubber according to the present invention contains a coupling center atom and also contains a high molecular weight component, a medium molecular weight component and a low molecular weight component so that the particle diameter of the low cis-polybutadiene rubber is three-stage distributed, and when used as a toughening agent for an aromatic vinyl resin, the three components synergistically interact with each other so that not only the aromatic vinyl resin has improved impact resistance but also the aromatic vinyl resin has good gloss.
According to the preparation method of the low cis-polybutadiene rubber, the low cis-polybutadiene rubber with different molecular weights does not need to be compounded, the coupling agent with different functionalities is not needed, the coupling agent with three functionalities is adopted, the coupling agent with three functionalities is excessive relative to an organolithium initiator, and the low cis-polybutadiene rubber containing the high molecular weight component, the medium molecular weight component and the low molecular weight component can be obtained through one-step coupling reaction.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a low cis-polybutadiene rubber comprising a coupling center atom, a high molecular weight component, a medium molecular weight component and a low molecular weight component, the high molecular weight component having a number average molecular weight (M n ) 210,000-360,000, preferably 230,000-350,000, more preferablyPreferably 240,000-330,000, further preferably 270,000-320,000; the number average molecular weight of the medium molecular weight component is 150,000-250,000, preferably 160,000-240,000, more preferably 170,000-230,000, and even more preferably 180,000-220,000; the low molecular weight component has a number average molecular weight of 80,000 to 120,000, preferably 85,000 to 115,000, more preferably 90,000 to 110,000. The low cis-polybutadiene rubber according to the present invention has a number average molecular weight size relationship among the high molecular weight component, the medium molecular weight component and the low molecular weight component: the number average molecular weight of the high molecular weight component > the number average molecular weight of the medium molecular weight component > the number average molecular weight of the low molecular weight component.
According to the low cis-polybutadiene rubber of the present invention, the molecular weight distribution index (M w /M n ) May be 1 to 1.1, preferably 1.02 to 1.08; the molecular weight distribution index of the medium molecular weight component may be 1 to 1.1, preferably 1.02 to 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 low cis-polybutadiene rubber according to the present invention, the high molecular weight component is contained in an amount of 4 to 55% by weight, preferably 12 to 55% by weight, more preferably 15 to 50% by weight, still more preferably 18 to 45% by weight, based on the total amount of the low cis-polybutadiene rubber; the content of the medium molecular weight component is 25 to 50 wt%, preferably 30 to 50 wt%, more preferably 35 to 48 wt%, still more preferably 40 to 45 wt%; the content of the low molecular weight component is 5 to 70% by weight, preferably 7 to 60% by weight, more preferably 10 to 50% by weight, still more preferably 15 to 42% by weight.
The number average molecular weight of the low cis-polybutadiene rubber according to the present invention may be 130,000-230,000, preferably 150,000-210,000. The molecular weight distribution index of the low cis-polybutadiene rubber according to the present invention may be 1.3 to 2.3, preferably 1.5 to 2.1. In the present invention, the number average molecular weight and the molecular weight distribution index of the low cis-polybutadiene rubber refer to the overall number average molecular weight and the overall molecular weight distribution index of the low cis-polybutadiene rubber.
In the invention, the number average molecular weight and the molecular weight distribution index are measured by adopting a gel permeation chromatography, and the mass percentage of the high molecular weight component, the medium molecular weight component and the low molecular weight component is measured by adopting the gel permeation chromatography. The gel permeation chromatography analysis adopts an HLC-8320 gel permeation chromatograph of Tosoh corporation, wherein a chromatographic column is TSKgel SuperMultiporeHZ-N TSKgel SuperMultiporeHZ standard column, a solvent is chromatographic pure Tetrahydrofuran (THF), narrow-distribution polystyrene is used as a standard sample, a polymer sample is prepared into tetrahydrofuran solution with the mass concentration of 1mg/mL, the sample injection amount is 10.00 mu L, the flow rate is 0.35mL/min, and the test temperature is 40.0 ℃. The mass percent of the high molecular weight component, the medium molecular weight component and the low molecular weight component is calculated by the following steps:
the mass percent (%) of the high molecular weight component=the peak area of the peak corresponding to the high molecular weight component/(the peak area corresponding to the high molecular weight component+the peak area corresponding to the medium molecular weight component+the peak area corresponding to the low molecular weight component) in the GPC curve;
mass percent (%) of medium molecular weight component = peak area of peak corresponding to medium molecular weight component/(peak area corresponding to high molecular weight component + peak area corresponding to medium molecular weight component + peak area corresponding to low molecular weight component) in GPC curve;
The mass percent (%) of the low molecular weight component=the peak area of the peak corresponding to the low molecular weight component/(the peak area corresponding to the high molecular weight component+the peak area corresponding to the medium molecular weight component+the peak area corresponding to the low molecular weight component) in the GPC curve;
in the present invention, the peak area of the peak of each component is a percentage of the normalized peak area obtained by GPC testing.
The viscosity of the low cis-polybutadiene rubber according to the present invention in a 5 wt% styrene solution at 25℃may be 90cP or more, preferably 100 to 200cP, more preferably 110 to 180cP, still more preferably 115 to 170cP.
The low cis-polybutadiene rubber according to the present invention has a reduced 5 wt% styrene solution viscosity at 25℃and thus has better processability than the compounding of a linear low cis-polybutadiene rubber having a component corresponding to the high molecular weight, a linear low cis-polybutadiene rubber having a component corresponding to the medium molecular weight, and a linear low cis-polybutadiene rubber having a component corresponding to the low molecular weight. According to the low cis-polybutadiene rubber of the present invention, the viscosity of the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25℃is X centipoise, the viscosity of the low molecular weight component in the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25℃is Y centipoise, and the ratio of X/Y may be 1 to 1.5, for example: 1. 1.1, 1.2, 1.3, 1.4 or 1.5, preferably 1.1-1.4. The ratio of the viscosity to Y in a 5 wt% styrene solution at 25℃of a compound obtained by compounding a linear low cis-polybutadiene rubber having a component corresponding to the high molecular weight, a linear low cis-polybutadiene rubber having a component corresponding to the medium molecular weight, and a linear low cis-polybutadiene rubber having a component corresponding to the low molecular weight is usually 3 or more.
In the present invention, the viscosity of the rubber in a 5 wt% styrene solution at 25℃is determined according to the Q/SHYS.3155.SXJC06-2016 standard.
The low cis-polybutadiene rubber according to the present invention may have a Mooney viscosity at 100℃of 40 to 70, preferably 45 to 65, more preferably 48 to 60.
In the invention, the Mooney viscosity is measured by an SMV-201SK-160 Mooney viscometer manufactured by Shimadzu corporation according to the method specified in the national standard GB/T1232-92, and the test mode is as follows: ML (1+4), the test temperature is 100 ℃.
The vinyl content of the low cis-polybutadiene rubber according to the present invention may be 8 to 20% by weight, preferably 10 to 16% by weight.
The cis 1, 4-structural unit content of the low cis polybutadiene rubber according to the present invention may be 30 to 40 wt%.
In the present invention, the vinyl content means a structural unit formed by 1, 2-polymerization of butadiene, and in the present invention, cis 1, 4-structural unit means a structural unit formed by 1, 4-polymerization of butadiene and having a cis configuration. In the invention, the vinyl content and the cis 1, 4-structural unit content are measured by nuclear magnetic resonance spectroscopy, the solvent adopted in the test is deuterated chloroform, and tetramethyl silicon is used as an internal standard.
According to the low cis-polybutadiene rubber of the present invention, the low cis-polybutadiene rubber contains a coupling center atom. According to the low cis-polybutadiene rubber of the present invention, the coupling center atom may be provided by a coupling agent. According to the low cis-polybutadiene rubber of the present invention, the high molecular weight component and the medium 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 low cis-polybutadiene rubber of the present invention, the high molecular weight component and the medium molecular weight component are coupled polymers, which are components formed by reacting a coupling agent with the active end groups of the corresponding linear polymers, and linking at least two linear polymer chains together through the coupling center atom of the coupling agent.
The low cis-polybutadiene rubber according to the present invention may have a mass content of the coupling center atom of 88 to 245ppm based on the total amount of the low cis-polybutadiene rubber, for example: 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, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, or 245ppm, preferably 110 to 220ppm, more preferably 120 to 210ppm.
According to the low cis-polybutadiene rubber of the present invention, the coupling center atom is derived from a coupling agent, which is preferably one or two or more of trifunctional coupling agents. Preferably, the coupling agent is one or more than two of the coupling agents shown in the formula I,
Figure BDA0002067355340000081
in the formula I, R 1 Is C 1 -C 6 Alkyl group of (C) including 1 -C 6 Straight chain alkyl and C 3 -C 6 Specific examples of the branched alkyl group of (a) 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.
In the formula I, R 2 、R 3 And R is 4 Are dissociating groups, i.e. groups which react as reactive groups with the reactive end groups of the living polymer chains in the coupling reaction. In the formula I, R 2 、R 3 And R is 4 Preferably a halogen group, more preferably chlorine.
In formula I, Z is a coupling center atom, preferably a silicon atom or a tin atom, more preferably a silicon atom.
Specific examples of the coupling agent according to the low cis-polybutadiene rubber of the present invention may include, but are not limited to: one or more of methyltrichlorosilane, ethyltrichlosilane and methyltribromosilane. Preferably, the coupling agent is methyltrichlorosilane and/or ethyltrichlorosilane.
According to the low cis-polybutadiene rubber of the present invention, the high molecular weight component and the medium molecular weight component contain a coupling center atom. According to the low cis-polybutadiene rubber of the present invention, in addition to the coupling agent residues contained in the molecular chains of the high molecular weight component and the medium molecular weight component, at least part of the molecular chains of the low molecular weight component also contain coupling agent residues (i.e., at least part of the low molecular weight component contains a coupling center atom), except that the coupling agent residues in the molecular chains of the low molecular weight component are bonded to only one polymer chain.
The low cis-polybutadiene rubber according to the present invention has a coupling center atom content of N in mole percent Z The mole percent of the high molecular weight component is N H The molar percentage of the medium molecular weight component is N M The mole percent of the low molecular weight component is N L The coupling arm number of the high molecular weight component is A H The coupling arm number of the medium molecular weight component is A M ，3(N H +N M +N L )≥(N Z ×3)≥(N H ×A H +N M ×A M +N L ). Preferably, (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1-2.8, 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 or 2.8. More preferably, (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1.1-2.5. Further preferably, (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1.3-2.2. Still more preferably, (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1.4-1.8.
In the invention, the mass percent of the coupling center atoms is measured by a plasma method (ICP method), and the mole percent of the coupling center atoms is converted from the mass percent. In the invention, the mole percentage content and the coupling arm number of the high molecular weight component, the medium molecular weight component and the low molecular weight component are measured by adopting a GPC method, and the specific method is as follows:
number of coupling arms of high molecular weight component = number average molecular weight of high molecular weight component/number average molecular weight of low molecular weight component;
number of coupling arms of medium molecular weight component = number average molecular weight of medium molecular weight component/number average molecular weight of low molecular weight component;
the molar percentage 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 medium molecular weight component/number average molecular weight of the medium molecular weight component + peak area corresponding to the low molecular weight component/number average molecular weight of the low molecular weight component);
the molar percentage of the medium molecular weight component = (peak area corresponding to the medium molecular weight component/number average molecular weight of the medium 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 medium molecular weight component/number average molecular weight of the medium molecular weight component + number average molecular weight of the low molecular weight component);
The molar percentage 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 medium molecular weight component/number average molecular weight of the medium molecular weight component + number average molecular weight of the low molecular weight component).
The low cis-polybutadiene rubber according to the present invention may further contain at least one auxiliary agent to impart new properties to the low cis-polybutadiene rubber and/or to improve the properties of the low cis-polybutadiene rubber. The auxiliary agent may include an antioxidant. The type of the antioxidant is not particularly limited and may be conventionally selected, 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) orthocresol (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-isopropyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010 NA), and N-phenyl-2-naphthylamine (trade name: antioxidant D), preferably antioxidant 1520 and antioxidant 1076. When the antioxidant 1520 and the antioxidant 1076 are used in combination, the weight ratio of the antioxidant 1520 and the antioxidant 1076 may be 1:1-3. The antioxidant may be used in amounts conventional in the art. In one embodiment, the weight ratio of the antioxidant to the low cis 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 low cis-polybutadiene rubber, comprising the steps of:
(1) Polymerizing 1, 3-butadiene in an organic solvent in the presence of an organolithium initiator and a structure regulator under anionic polymerization conditions to obtain a polymerization solution containing polybutadiene;
(2) The polymerization solution is contacted with a coupling agent for coupling reaction to obtain a coupled polymer solution, the coupling agent is one or more than two of trifunctional coupling agents, and the molar weight of the coupling agent is n C The molar amount of the organolithium initiator is n I ，(2.1×n I )≥(n C ×3)＞n I 。
In the step (1), the organolithium initiator may be various organolithium compounds capable of initiating butadiene polymerization, which are commonly used in the field of anionic polymerization, preferably compounds represented by formula II,
R 5 li (formula II)
In formula II, R 5 Is C 1 -C 6 Alkyl, C of (2) 3 -C 12 Cycloalkyl, C 7 -C 14 Aralkyl or C of (C) 6 -C 12 Aryl groups of (a).
The C is 1 -C 6 The alkyl group of (C) includes C 1 -C 6 Straight chain alkyl and C 3 -C 6 Specific examples of the branched alkyl group of (a) 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.
The C is 3 -C 12 Specific examples of cycloalkyl groups of (2)May include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
The C is 7 -C 14 Specific examples of aralkyl groups 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.
The C is 6 -C 12 Specific examples of aryl groups 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 ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, cyclohexyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butylphenyl lithium, 4-tolyl lithium and 4-butylcyclohexyl lithium. Preferably, the organolithium initiator is n-butyllithium and/or sec-butyllithium. More preferably, the organolithium initiator is n-butyllithium.
In step (1), the molecular weight of the polybutadiene can be adjusted by adjusting the ratio between the organolithium initiator and 1, 3-butadiene. According to the preparation method of the present invention, in a preferred embodiment, the molar ratio of 1, 3-butadiene to the organolithium initiator is 1400-2300:1. in this preferred embodiment, the molar ratio of 1, 3-butadiene to the organolithium initiator is more preferably from 1500 to 2200:1, further preferably 1600-2100:1. 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 modifier is used for adjusting the vinyl content in the polybutadiene formed by polymerization, and can be one or more than two of an ether type structure modifier and an amine type structure modifier.
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 may be one or more of an aliphatic symmetric monoether and an aliphatic asymmetric monoether. Specific examples of the aliphatic monoethers may include, but are not limited to: one or more of methyl ether, diethyl ether, propyl ether and methyl diethyl ether.
The aliphatic polyether may 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 C 1 -C 4 Alkyl, such as methyl, ethyl, n-propyl, isopropyl, 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-dioxane. Specific examples of the cyclic ether may include, but are not limited to: one or more of tetrahydrofuran, tetrahydrofurfurylmethyl ether, tetrahydrofurfurylethyl ether, tetrahydrofurfurylpropyl ether, tetrahydrofurfurylbutyl ether and 1, 4-dioxane.
The amine structure regulator can be one or more of N, N, N ', N' -tetramethyl ethylenediamine, N, N-dimethyl tetrahydrofurfuryl amine, triethylamine and tripropylamine.
In a preferred embodiment, the structure modifier in step (1) is one or more of tetrahydrofuran, tetrahydrofurfuryl alkyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether and amine type structure modifier, and the alkyl group may be C 1 -C 4 Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. In this preferred embodiment, the structure-modifying agent is preferably tetrahydrofuran, tetrahydrofurfurylmethyl ether, tetrahydrofurfurylethyl ether, tetrahydrofurfurylpropyl ether, tetrahydrofurfurylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl etherOne or more than two of ethylene glycol diethyl ether and N, N-dimethyl tetrahydrofurfuryl amine; more preferably one or more of tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether and tetrahydrofurfuryl propyl ether.
In step (1), the amount of the structure-modifying agent may be conventionally selected. In step (1), the molar ratio of the structure modifier to the organolithium initiator may be 0.01 to 1:1, preferably 0.02-0.8:1, more preferably 0.05 to 0.7:1.
In the step (1), the polymerization is carried out in an organic solvent, which may be various organic substances capable of being used as a reaction medium and allowing the polymerization to proceed under the condition of solution polymerization, 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 distillate oil which is remained after aromatic hydrocarbon is extracted from catalytic reforming products rich in aromatic hydrocarbon in the petroleum refining process. The amount of the solvent may be conventional in the art. Generally, in step (1), the solvent may be used in an amount such that the concentration of 1, 3-butadiene is 1 to 25% by weight, preferably 10 to 20% by weight.
In step (1), the polymerization may be carried out under conventional anionic polymerization conditions. The polymerization in step (1) results in a conversion of 1, 3-butadiene of 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 from 20 to 80 minutes, preferably from 30 to 60 minutes. In step (1), the polymerization may be carried out at a pressure of 0.1 to 1MPa, preferably at a pressure of 0.2 to 0.5MPa, the pressure being gauge pressure.
According to the preparation method of the invention, in the step (2), the coupling agent is used in an excessive amount, and the molar amount of the organic lithium initiator is n I ，(2.1×n I )≥(n C ×3)＞n I . According to the preparation method of the invention, the polybutadiene rubber with different molecular weights can be obtained through one-step coupling reaction by adopting excessive coupling agent,avoiding the use of more than two coupling agents or compounding polybutadiene rubber with different molecular weights. Preferably n C /n I The ratio of (2) is 0.38-0.7:1, controlling the amount of the coupling agent and the organolithium initiator in this ratio can further improve the properties of the finally prepared polybutadiene rubber as a toughening agent for an aromatic vinyl resin, so that the aromatic vinyl resin obtains a better balance of properties between impact resistance and optical properties. More preferably, n C /n I The ratio of (2) is 0.42-0.65:1. further preferably, n C /n I The ratio of (2) is 0.45-0.6:1.
in the step (2), the coupling agent is one or more than two of trifunctional coupling agents.
Preferably, the coupling agent is one or more than two of the coupling agents shown in the formula I,
Figure BDA0002067355340000131
in the formula I, R 1 Is C 1 -C 6 Alkyl group of (C) including 1 -C 6 Straight chain alkyl and C 3 -C 6 Specific examples of the branched alkyl group of (a) 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.
In the formula I, R 2 、R 3 And R is 4 Are dissociating groups, i.e. groups which react as reactive groups with the reactive end groups of the living polymer chains in the coupling reaction. In the formula I, R 2 、R 3 And R is 4 Preferably a halogen group, more preferably chlorine.
In formula I, Z is a coupling center atom, preferably a silicon atom or a tin atom, more preferably a silicon atom.
Specific examples of the coupling agent may include, but are not limited to: one or more of methyltrichlorosilane, ethyltrichlosilane and methyltribromosilane. Preferably, the coupling agent is methyltrichlorosilane and/or ethyltrichlorosilane.
According to the preparation method of the present invention, in the step (2), the coupling reaction may be performed at a temperature of 50 to 100 ℃, preferably 60 to 80 ℃. The duration of the coupling reaction may be 20-40 minutes. The coupling reaction may be carried out at a pressure of 0.1 to 1MPa, preferably 0.2 to 0.5MPa, the pressure being gauge pressure.
The preparation method according to the present invention preferably further comprises a step (3) of contacting the coupled polymer solution with a terminator to perform a termination reaction to obtain a termination reaction solution.
The terminator may be various substances capable of terminating an active chain, which are commonly used in the field of anionic polymerization. The terminator may be C 1 -C 4 One or more of isopropanol, stearic acid, citric acid and carbon dioxide, more preferably carbon dioxide. Carbon dioxide is adopted for termination reaction, and can form carbonate with metal ions (Li, mg, al, fe and Zn) in a polymerization system to be separated from a polymer, so that the color reaction of the metal ions is avoided, and the product has lower chromaticity. The carbon dioxide may be introduced into the reaction system in the form of a gas (e.g., a 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 (e.g., a concentration of 0.1 to 5% by weight).
The preparation method according to the invention can further comprise the step (4): adding at least one auxiliary agent to the termination reaction liquid obtained in the step (3) to endow the finally prepared low cis-polybutadiene rubber with new properties and/or improve the properties of the finally prepared low cis-polybutadiene rubber.
In particular, the auxiliary agent may include an antioxidant. The type of the antioxidant is not particularly limited and may be conventionally selected, 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) orthocresol (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-isopropyl-N' -phenyl-p-phenylenediamine (trade name: antioxidant 4010 NA), and N-phenyl-2-naphthylamine (trade name: antioxidant D), preferably antioxidant 1520 and antioxidant 1076. When the antioxidant 1520 and the antioxidant 1076 are used in combination, the weight ratio of the antioxidant 1520 and the antioxidant 1076 may be 1:1-3. The antioxidant may be used in amounts conventional in the art. In one embodiment, the weight ratio of the antioxidant to 1, 3-butadiene may be 0.1 to 0.4:100.
According to the preparation method of the present invention, the obtained mixture may be purified and separated by a conventional method to obtain the low cis-polybutadiene rubber. Specifically, the resulting mixture may be subjected to centrifugal separation, filtration, decantation or hot water coagulation to obtain a low cis-polybutadiene rubber; the resulting mixture may also be stripped to remove the solvent therefrom, thereby obtaining a low cis-polybutadiene rubber.
The polymerization method according to 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-polybutadiene rubber produced by the production method according to the second aspect of the present invention.
The low cis-polybutadiene rubber prepared by the method of the second aspect of the invention can obtain a high molecular weight component, a medium molecular weight component and a low molecular weight component by controlling the dosage of the coupling agent to be excessive without compounding.
Specifically, according to the low cis-polybutadiene rubber of the third aspect of the present invention, the low cis-polybutadiene rubber contains a high molecular weight component, a medium molecular weight component and a low molecular weight component, and the number average molecular weight of the high molecular weight component may be 210,000-360,000, preferably 230,000-350,000, more preferably 240,000-330,000, still more preferably 270,000-320,000; the number average molecular weight of the medium molecular weight component may be 150,000-250,000, preferably 160,000-240,000, more preferably 170,000-230,000, still more preferably 180,000-220,000; the low molecular weight component may have a number average molecular weight of 80,000 to 120,000, preferably 85,000 to 115,000, more preferably 90,000 to 110,000. According to the low cis-polybutadiene rubber of the third aspect of the present invention, the number average molecular weight size relationship of the high molecular weight component, the medium molecular weight component and the low molecular weight component is: the number average molecular weight of the high molecular weight component > the number average molecular weight of the medium molecular weight component > the number average molecular weight of the low molecular weight component.
According to the low cis-polybutadiene rubber of the third aspect of the present invention, the molecular weight distribution index (M w /M n ) May be 1 to 1.1, preferably 1.02 to 1.08; the molecular weight distribution index of the medium molecular weight component may be 1 to 1.1, preferably 1.02 to 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 low cis-polybutadiene rubber according to the third aspect of the present invention may contain the high molecular weight component in an amount of 4 to 55 wt%, preferably 12 to 55 wt%, more preferably 15 to 50 wt%, still more preferably 18 to 45 wt%, based on the total amount of the low cis-polybutadiene rubber; the medium molecular weight component may be present in an amount of 25 to 50 wt%, preferably 30 to 50 wt%, more preferably 35 to 48 wt%, and even more preferably 40 to 45 wt%; the low molecular weight component may be present in an amount of 5 to 70 wt%, preferably 7 to 60 wt%, more preferably 10 to 50 wt%, still more preferably 15 to 42 wt%.
The low cis-polybutadiene rubber according to the third aspect of the present invention may have a number average molecular weight of 130,000-230,000, preferably 150,000-210,000. The molecular weight distribution index of the low cis-polybutadiene rubber according to the third aspect of the present invention may be 1.3 to 2.3, preferably 1.5 to 2.1.
According to a fourth aspect of the present invention there is provided the use of a low cis polybutadiene rubber according to the first or third aspect of the present invention as an aromatic vinyl resin toughening agent.
The low cis-polybutadiene rubber according to the present invention can be added to an aromatic vinyl resin as a toughening agent by conventional methods, for example: the low cis polybutadiene rubber may be added during polymerization to form an aromatic vinyl resin, or the low cis polybutadiene rubber may be added as a toughening agent to the aromatic vinyl resin.
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 low cis polybutadiene rubber according to the first or third aspect of the present invention.
The aromatic vinyl base resin may be a polymer formed by homo-or copolymerizing an aromatic vinyl monomer, which refers to a monomer having both an aryl 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 a combination of more than two of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and vinyl naphthalene. Preferably, the aromatic vinyl monomer is styrene.
A preferred example of the aromatic vinyl resin is high impact polystyrene.
The amount of the low cis-polybutadiene rubber as the toughening agent may be conventionally selected. Specifically, the low cis-polybutadiene rubber may be used in an amount of 5 to 15 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 low cis polybutadiene rubber according to the first or third aspect of the present invention.
According to the method for preparing an aromatic vinyl resin of the present invention, specific examples of the aromatic vinyl monomer may include, but are not limited to: one or a combination of more than two of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and vinyl naphthalene. Preferably, the aromatic vinyl monomer is styrene.
According to the method for producing an aromatic vinyl resin of the present invention, the polymerization reaction can be carried out by a radical polymerization method. The type of the radical initiator used for the radical polymerization is not particularly limited, and may be selected conventionally, and for example, one or two or more of the radical initiators may be used. Preferably, the free radical initiator is one or more than two of peroxide type initiator and azo-bis-nitrile type initiator. Specific examples of the radical initiator may include, but are not limited to: one or more of diacyl peroxide, tert-butyl peroxy-2-ethylhexyl carbonate, peroxydicarbonate, peroxycarboxylate, alkyl peroxide and azodinitrile compound (such as azodiisobutyronitrile and azodiisoheptanenitrile). Preferably, the free radical initiator is one or more of dibenzoyl peroxide, di-o-methylbenzoyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxy-2-ethylhexyl carbonate.
The amount of the radical initiator 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 based on the desired molecular weight of the polymer are well known to those skilled in the art and will not be described in detail herein.
According to the method for producing an aromatic vinyl resin of the present invention, the polymerization reaction can be carried out under conventional conditions. Generally, the polymerization conditions include: the temperature may be 100-170℃and the time may be 4-12 hours (e.g., 7-9 hours). Preferably, the polymerization reaction may 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 to 125 ℃, and the duration of the first polymerization reaction may be 3 to 4 hours; the second polymerization reaction may be performed at a temperature of 130 to 140 ℃, and the duration of the second polymerization reaction may be 1 to 3 hours; the third polymerization reaction may be performed at a temperature of 150 to 160 ℃, and the duration of the third polymerization reaction may be 0.5 to 1.5 hours; the fourth polymerization reaction may be performed at a temperature of 165-175 ℃ and the duration of the fourth polymerization reaction may be 0.5-1.5 hours.
The high impact polystyrene according to the present invention has excellent impact resistance, and the Izod impact strength thereof may be 13kJ/m 2 Above (e.g. 13-20 kJ/m) 2 ) Typically 15kJ/m 2 Above (e.g. 15-20 kJ/m) 2 ) Preferably 17kJ/m 2 The above; the 60 ° surface gloss may be 55 or more, typically 62 or more, preferably 65 or more, for example: 68-75.
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 to the monomer charge.
In the following examples and comparative examples, the content of 1, 2-polymeric structural units in the low cis-polybutadiene rubber was determined by AVANCEDRX400MHz nuclear magnetic resonance apparatus manufactured by BRUKER, wherein the frequency was 400MHz, the solvent was deuterated chloroform, and the built-in standard sample was tetramethylsilane. Gel permeation chromatography was performed on a model HLC-8320 gel permeation chromatograph from eastern co., japan, wherein the test conditions include: the chromatographic column is TSKgel SuperMultiporeHZ-N, the standard column is TSKgel SuperMultiporeHZ, the solvent is chromatographic pure THF, the calibration standard sample is polystyrene, the mass concentration of the sample is 1mg/mL, the sample injection amount is 10.00 mu L, the flow rate is 0.35mL/min, and the test temperature is 40 ℃. Plasma analysis (ICP) was performed on an ICPMS-2030 instrument available from Shimadzu, which was measured according to the GB/T18174-2000 standard.
In the following examples and comparative examples, the styrene solution viscosity of 5 wt% 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, mooney viscosity was measured using a SMV-201SK-160 rotor-free Mooney viscometer manufactured by Shimadzu corporation, wherein the preheating time was 1min, the rotation time was 4min, and the test temperature was 100 ℃.
In the following examples and comparative examples, chromaticity was measured according to the Q/SH 3165 251-2014 standard, and test conditions include: the color system is CIELAB, the optical geometry is 45/0, the light source is C light source, the observation angle is 2 degrees, and the diameter of the observation hole is 30mm.
In the following examples and comparative examples, the mechanical properties were tested using an INSTRON 5567 Universal materials tester in England, in which the notched Izod impact strength was measured according to GB/T1843-1996 standard (kJ/m 2 ). In the following examples and comparative examples, 60 ° gloss is 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 purchased from Inonoka reagent company, tetrahydrofurfuryl ethyl ether was purchased from carbofuran reagent company, methyltrichlorosilane, ethyltrichlorosilane and dimethyldichlorosilane were purchased from carbofuran reagent company (analytically pure, diluted to a concentration of 0.1 mol/L), n-butyllithium and sec-butyllithium were purchased from carbofuran reagent company, and hexane was used to a concentration of 0.4mol/L, respectively.
Examples 1-9 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 a polymerization reaction temperature, adding an organolithium 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) To the polymerization reaction mixture was added an excessive amount of a trifunctional coupling agent (specific kind and amount are listed in Table 2), and the coupling reaction was carried out under the conditions listed in Table 2 (coupling reaction temperature, pressure and time are shown in Table 2), to obtain a coupling reaction mixture.
(3) After the completion of the coupling reaction, a terminating agent (specific kind and amount are 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 low cis-polybutadiene rubber. The resulting polymerization solution was subjected to steam coagulation desolventizing treatment and dried to obtain a low cis-polybutadiene rubber, the structure and property parameters of which are shown in tables 3 and 4.
Examples 2 to 9
A low cis-polybutadiene rubber was prepared by the same procedures as in example 1, except that the conditions shown in tables 1 and 2 were used, respectively, to obtain low cis-polybutadiene rubbers, and the structure and property parameters of the obtained low cis-polybutadiene rubbers are shown in tables 3 and 4.
Comparative example 1
A low cis-polybutadiene rubber was prepared by the same procedures as in example 1, except that the amount of the coupling agent in step (2) was as shown in Table 2, and the structure and property parameters of the obtained low cis-polybutadiene rubber were as shown in tables 3 and 4.
Comparative example 2
A low cis-polybutadiene rubber was prepared by the same procedures as in example 1, except that the amount of the coupling agent in step (2) was as shown in Table 2, and the structure and property parameters of the obtained low cis-polybutadiene rubber were as shown in tables 3 and 4.
Comparative example 3
A low cis-polybutadiene rubber was prepared by the same procedures as in example 1, except that in step (2), methyltrichlorosilane as a coupling agent was replaced with an equimolar amount of dimethyldichlorosilane. The structure and property parameters of the resulting low cis-polybutadiene rubber are shown in tables 3 and 4.
Comparative example 4
A low cis-polybutadiene rubber was prepared by the same procedures as in example 1, except that the amount of n-butyllithium as an initiator in step (1) was 8mmol, and the amount of methyltrichlorosilane in step (2) was 3.6mmol. The structure and property parameters of the resulting low cis-polybutadiene rubber are shown in tables 3 and 4.
Comparative example 5
Low cis-polybutadiene linear polymers having number average molecular weights of 9.3 tens of thousands, 18.8 tens of thousands and 27.2 tens of thousands were prepared by the same procedures as in the steps (1) and (3) of example 1, respectively (specific reaction conditions are shown in tables 1 and 3), and the three linear polymers were mixed at a mass ratio of 9.3 tens of thousands/18.8 tens of thousands/27.2 tens of thousands=2.43/2.56/1 to obtain low cis-polybutadiene rubber linear copolymers, the structure and property parameters of which are shown in tables 3 and 4.
TABLE 1
Figure BDA0002067355340000221
TABLE 2
Figure BDA0002067355340000231
TABLE 3 Table 3
Figure BDA0002067355340000241
1 : the sum of areas of the peak corresponding to the high molecular weight component (i.e., the first peak), the peak corresponding to the medium molecular weight component (i.e., the second peak), and the peak corresponding to the low molecular weight component (i.e., the third peak) in the GPC curve is taken as a reference.
TABLE 4 Table 4
Figure BDA0002067355340000242
1 : X/Y, X is the viscosity of the low cis-polybutadiene rubber prepared in this example or comparative example in a 5 wt% styrene solution at 25℃and Y is the viscosity of the low molecular weight component in the low cis-polybutadiene rubber prepared in this example or comparative example in a 5 wt% styrene solution at 25 ℃.
2 : the measurement was performed by a plasma method.
3 ：A H Number average molecular weight of high molecular weight component/number average molecular weight of low molecular weight component;
A M number average molecular weight of medium molecular weight component/number average molecular weight of low molecular weight component;
N H = (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 medium molecular weight component/number average molecular weight of medium molecular weight component + peak area corresponding to low molecular weight component/number average molecular weight of low molecular weight component);
N M = (peak area corresponding to medium molecular weight component/number average molecular weight of medium molecular weight component)/(peak area corresponding to high molecular weight component/number average molecular weight of high molecular weight component + peak area corresponding to medium molecular weight component/number average molecular weight of medium molecular weight component + peak area corresponding to low molecular weight component/number average molecular weight of low molecular weight component);
N L = (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 medium molecular weight component/number average molecular weight of medium molecular weight component + number average molecular weight of low molecular weight component).
As can be seen from Table 4, in the low cis-polybutadiene rubber according to the present invention, the 3-fold coupling of the content of the central atom with (N) H ×A H +N M ×A M +N L ) The ratio of (2) is greater than 1, indicating that in the low cis-polybutadiene rubber according to the present invention, most of the molecular chains contain coupling center atoms, i.e., not only the molecular chains of the high-molecular-weight component and the medium-molecular-weight component formed by coupling contain coupling center atoms, but also the molecular chains of the low-molecular-weight component substantially contain coupling center atoms. As can be seen by comparing example 1 with comparative example 5, the low cis-polybutadiene rubber according to the present inventionThe resulting mixture has a reduced viscosity and thus better processability than a mixture of three linear polymers. It can also be seen from Table 4 that the low cis-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 to 9 HIPS resin was prepared by using the low cis-polybutadiene rubber prepared in examples 1 to 9 as a toughening agent, respectively, and the proportion of the toughening agent relative to the styrene monomer was 8% by using a conventional bulk method, to obtain high impact polystyrene, and the specific polymerization method was:
the toughening agent, the styrene and the free radical initiator are mixed, polymerization is carried out with stirring, after the polymerization reaction is completed, the reaction product is subjected to vacuum flash evaporation to remove unreacted monomers and solvent, and then the high-impact polystyrene is obtained, 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
A high impact polystyrene was prepared in the same manner as in experimental example 1, except that the tougheners were low cis polybutadiene prepared in comparative examples 1 to 5, respectively. The polymerization conditions are set forth in Table 5 and the performance parameters of the high impact polystyrene prepared are set forth in Table 6.
Experimental comparative examples 6 to 7
High impact polystyrene was prepared in the same manner as experimental example 1, except that the toughening agents were prepared using the japanese asahi chemical industry products 720A and 730A, respectively (solvent removed). The polymerization conditions are set forth in Table 5 and the performance parameters of the high impact polystyrene prepared are set forth 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 produced are listed in table 6.
TABLE 5
Figure BDA0002067355340000261
TABLE 6
Numbering device Notched Izod impact Strength (kJ/m) 2 ) Surface gloss (60 degree)
Experimental example 1 17.2 73
Experimental example 2 17.6 69
Experimental example 3 18.3 72
Experimental example 4 17.9 71
Experimental example 5 17.2 69
Experimental example 6 15.4 68
Experimental example 7 15.8 63
Experimental example 8 15.2 62
Experimental example 9 13.8 59
Experiment comparative example 1 12.6 62
Experiment comparative example 2 6.9 65
Experiment comparative example 3 11.5 62
Experiment comparative example 4 8.7 74
Experiment comparative example 5 14.9 42
Experiment comparative example 6 7.9 79
Experiment comparative example 7 10.8 74
Experimental reference example 1 1.2 94
As can be seen from the results of Table 6, the high impact polystyrene prepared by using the low cis-polybutadiene rubber of the present invention as a toughening agent has good impact resistance, while maintaining good gloss.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (64)

1. A low cis-polybutadiene rubber comprising a coupling center atom, a high molecular weight component having a number average molecular weight of 210,000-360,000, a medium molecular weight component having a number average molecular weight of 150,000-250,000, and a low molecular weight component having a number average molecular weight of 80,000 to 120,000, the relationship between the number average molecular weights of the high, medium and low molecular weight components being: the high molecular weight component has a number average molecular weight of > the medium molecular weight component has a number average molecular weight of > the low molecular weight component, the high molecular weight component is contained in an amount of 4 to 55% by weight, the medium molecular weight component is contained in an amount of 25 to 50% by weight, the low molecular weight component is contained in an amount of 5 to 70% by weight, and the low cis-polybutadiene rubber has a number average molecular weight of 130,000-230,000 based on the total amount of the low cis-polybutadiene rubber.
2. The low cis-polybutadiene rubber according to claim 1, wherein the high molecular weight component has a number average molecular weight of 230,000-350,000, the medium molecular weight component has a number average molecular weight of 160,000-240,000, and the low molecular weight component has a number average molecular weight of 85,000-115,000.
3. The low cis-polybutadiene rubber according to claim 2, wherein the high molecular weight component has a number average molecular weight of 240,000-330,000, the medium molecular weight component has a number average molecular weight of 170,000-230,000, and the low molecular weight component has a number average molecular weight of 90,000-110,000.
4. The low cis-polybutadiene rubber according to claim 3, wherein the high molecular weight component has a number average molecular weight of 270,000-320,000; the number average molecular weight of the medium molecular weight component was 180,000-220,000.
5. The low cis-polybutadiene rubber according to claim 1 to 4, wherein the high molecular weight component has a molecular weight distribution index of 1 to 1.1, the medium molecular weight component has a molecular weight distribution index of 1 to 1.1, and the low molecular weight component has a molecular weight distribution index of 1 to 1.1.
6. The low cis-polybutadiene rubber according to claim 1 to 4, wherein the content of the high molecular weight component is 12 to 55 wt%, the content of the medium molecular weight component is 30 to 50 wt% and the content of the low molecular weight component is 7 to 60 wt%, based on the total amount of the low cis-polybutadiene rubber.
7. The low cis-polybutadiene rubber according to claim 1 to 4, wherein the content of the high molecular weight component is 15 to 50 wt%, the content of the medium molecular weight component is 35 to 48 wt% and the content of the low molecular weight component is 10 to 50 wt%, based on the total amount of the low cis-polybutadiene rubber.
8. The low cis-polybutadiene rubber according to claim 1 to 4, wherein the content of the high molecular weight component is 18 to 45 wt%, the content of the medium molecular weight component is 40 to 45 wt% and the content of the low molecular weight component is 15 to 42 wt%, based on the total amount of the low cis-polybutadiene rubber.
9. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the number average molecular weight of the low cis-polybutadiene rubber is 150,000-210,000.
10. The low cis-polybutadiene rubber according to any one of claims 1 to 4, wherein the molecular weight distribution index of the low cis-polybutadiene rubber is 1.3 to 2.3.
11. The low cis-polybutadiene rubber according to claim 1 to 4, wherein the viscosity of the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is 90cP or more.
12. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the viscosity of the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is 100-200cP.
13. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the viscosity of the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is 110-180cP.
14. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the viscosity of the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is 115-170cP.
15. The low cis-polybutadiene rubber of claim 12, wherein the viscosity of the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is X centipoise, the viscosity of the low molecular weight component in the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is Y centipoise, and the ratio of X/Y is 1 to 1.5.
16. The low cis-polybutadiene rubber of claim 12, wherein the viscosity of the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is X centipoise, the viscosity of the low molecular weight component in the low cis-polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is Y centipoise, and the ratio of X/Y is 1.1-1.4.
17. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the Mooney viscosity of the low cis-polybutadiene rubber at 100 ℃ is 40 to 70.
18. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the Mooney viscosity of the low cis-polybutadiene rubber at 100℃is 45-65.
19. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the Mooney viscosity of the low cis-polybutadiene rubber at 100 ℃ is 48 to 60.
20. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the vinyl content of the low cis-polybutadiene rubber is 8 to 20 wt%.
21. The low cis-polybutadiene rubber according to any of claims 1 to 4, wherein the vinyl content of the low cis-polybutadiene rubber is 10 to 16 wt%.
22. The low cis-polybutadiene rubber according to claim 1 to 4, wherein the cis-1, 4-structural unit content of the low cis-polybutadiene rubber is 30 to 40 wt%.
23. The low cis-polybutadiene rubber of claim 1, wherein the high molecular weight component and the medium molecular weight component contain coupling center atoms, at least a portion of the low molecular weight component contains coupling center atoms, and the low molecular weight component is a linear polymer.
24. The low cis-polybutadiene rubber according to claim 1, wherein the coupling central atom is a silicon atom and/or a tin atom.
25. The low cis-polybutadiene rubber according to claim 1, wherein the mass content of the coupling center atom is 88 to 245ppm based on the total amount of the low cis-polybutadiene rubber.
26. The low cis-polybutadiene rubber according to claim 1, wherein the mass content of the coupling center atom is 110 to 220ppm based on the total amount of the low cis-polybutadiene rubber.
27. The low cis-polybutadiene rubber according to claim 1, wherein the mass content of the coupling center atom is 120 to 210ppm based on the total amount of the low cis-polybutadiene rubber.
28. The low cis polybutadiene rubber of any of claims 23-27, wherein the coupling center atom is derived from a coupling agent that is one or more of a trifunctional coupling agent.
29. The low cis-polybutadiene rubber according to claim 28, wherein the coupling agent is one or more of the coupling agents represented by formula I,
Figure FDA0004119794750000051
in the formula I, R 1 Is C 1 -C 6 Alkyl of R 2 、R 3 And R is 4 Z is a coupling central atom for dissociating a group.
30. The low cis-polybutadiene rubber of claim 29, wherein in formula I, R 2 、R 3 And R is 4 Z is a silicon atom or a tin atom.
31. The low cis-polybutadiene rubber of claim 29, wherein in formula I, R 2 、R 3 And R is 4 Chlorine and Z is a silicon atom.
32. The low cis-polybutadiene rubber of claim 28, wherein the coupling agent is methyltrichlorosilane and/or ethyltrichlorosilane.
33. The low cis-polybutadiene rubber of claim 28, wherein the low cis-polybutadiene rubber has a mole percentage of coupling center atoms of N Z The mole percent of the high molecular weight component is N H The molar percentage of the medium molecular weight component is N M The mole percent of the low molecular weight component is N L The coupling arm number of the high molecular weight component is A H The coupling arm number of the medium molecular weight component is A M ，3(N H +N M +N L )≥(N Z ×3)≥(N H ×A H +N M ×A M +N L )。
34. The low cis-polybutadiene rubber of claim 33, wherein (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1-2.8.
35. The low cis-polybutadiene rubber of claim 33, wherein (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1.1-2.5.
36. The low cis-polybutadiene rubber of claim 33, wherein (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1.3-2.2.
37. The low cis-polybutadiene rubber of claim 33, wherein (N) Z ×3)/(N H ×A H +N M ×A M +N L ) The ratio of (2) is 1.4-1.8.
38. A process for preparing the low cis-polybutadiene rubber of claim 1, which comprises the steps of:
(1) Polymerizing 1, 3-butadiene in an organic solvent in the presence of an organolithium initiator and a structure regulator under anionic polymerization conditions to obtain a polymerization solution containing polybutadiene;
(2) The polymerization solution is contacted with a coupling agent for coupling reaction to obtain a coupled polymer solution, the coupling agent is one or more than two of trifunctional coupling agents, and the molar weight of the coupling agent is n C The molar amount of the organolithium initiator is n I ，(2.1×n I )≥(n C ×3)＞n I 。
39. The method according to claim 38, wherein in the step (2), n C /n I The ratio of (2) is 0.38-0.7:1.
40. the method according to claim 38, wherein in the step (2), n C /n I The ratio of (2) is 0.42-0.65:1.
41. the preparation of claim 38The method, wherein in the step (2), n C /n I The ratio of (2) is 0.45-0.6:1.
42. the production process according to any one of claims 38 to 41, 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, and the coupling reaction is carried out at a pressure of 0.1 to 1MPa, the pressure being a gauge pressure.
43. The process according to any one of claims 38 to 41, wherein the coupling agent is one or more of those represented by formula I,
Figure FDA0004119794750000071
in the formula I, R 1 Is C 1 -C 6 Alkyl of R 2 、R 3 And R is 4 Z is a coupling central atom for dissociating a group.
44. The process of claim 43, wherein R in formula I 2 、R 3 And R is 4 Z is a silicon atom or a tin atom.
45. The process of claim 43, wherein R in formula I 2 、R 3 And R is 4 Chlorine and Z is a silicon atom.
46. The process according to any one of claims 38 to 41, wherein the coupling agent is methyltrichlorosilane and/or ethyltrichlorosilane.
47. The process according to claim 38, wherein the organolithium initiator is a compound of formula II,
R 5 li (formula II)
In formula II, R 5 Is C 1 -C 6 Alkyl, C of (2) 3 -C 12 Cycloalkyl, C 7 -C 14 Aralkyl or C of (C) 6 -C 12 Aryl groups of (a).
48. The process of claim 38, wherein the organolithium initiator is one or more of ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyl lithium, cyclohexyl lithium, phenyl lithium, 2-naphthyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, and 4-butylcyclohexyl lithium.
49. The process according to any one of claims 38, 47 and 48, wherein in step (1), the molar ratio of 1, 3-butadiene to the organolithium initiator is 1400-2300:1.
50. the process of any one of claims 38, 47 and 48, wherein in step (1), the molar ratio of 1, 3-butadiene to organolithium initiator is from 1500 to 2200:1.
51. the method according to claim 38, wherein the structure-adjusting agent is one or more of an ether-type structure-adjusting agent and an amine-type structure-adjusting agent.
52. The method according to claim 38, wherein the structure-adjusting agent is one or more of tetrahydrofuran, tetrahydrofurfuryl alkyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, and amine-type structure-adjusting agent.
53. The process of claim 52, wherein said alkyl is C 1 -C 4 An alkyl group.
54. The preparation method of claim 38, wherein the structure regulator is one or more of tetrahydrofuran, tetrahydrofurfurylmethyl ether, tetrahydrofurfurylethyl ether, tetrahydrofurfurylpropyl ether, tetrahydrofurfurylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and N, N-dimethyl tetrahydrofurfuryl amine.
55. The method according to claim 38, wherein the structure-adjusting agent is one or more of tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether and tetrahydrofurfuryl propyl ether.
56. The process according to any one of claims 38 and 51 to 55, wherein in step (1), the molar ratio of the structure-modifying agent to the organolithium initiator is from 0.01 to 1:1.
57. the production method according to claim 38, wherein in the step (1), the polymerization is performed at a temperature of 0 to 100 ℃, the duration of the polymerization is 20 to 80 minutes, and the polymerization is performed at a pressure of 0.1 to 1MPa, the pressure being a gauge pressure.
58. The production process according to claim 38, wherein in the step (1), the polymerization is carried out at a temperature of 40 to 95 ℃, the duration of the polymerization is 30 to 60 minutes, and the polymerization is carried out at a pressure of 0.2 to 0.5MPa, the pressure being a gauge pressure.
59. The method of claim 38, further comprising the step (3) of contacting the coupled polymer solution with a terminating agent to effect a termination reaction.
60. The method of claim 59, wherein the terminator is C 1 -C 4 One or more of alcohol, organic acid and carbon dioxide.
61. The process of claim 59, wherein the terminator is one or more of isopropanol, stearic acid, citric acid and carbon dioxide.
62. Use of the low cis-polybutadiene rubber of any one of claims 1-37 as an aromatic vinyl resin toughening agent.
63. An aromatic vinyl resin comprising an aromatic vinyl matrix resin and a toughening agent, wherein the toughening agent is the low cis polybutadiene rubber of any one of claims 1 to 37.
64. A process for preparing an aromatic vinyl resin, the process comprising: polymerizing an aromatic vinyl monomer in the presence of a toughening agent, wherein the toughening agent is the low cis polybutadiene rubber of any one of claims 1 to 37.
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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
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
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
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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