CN111978446B

CN111978446B - Polybutadiene rubber, preparation method and application thereof, and aromatic vinyl resin and preparation method thereof

Info

Publication number: CN111978446B
Application number: CN201910425475.8A
Authority: CN
Inventors: 李建成; 徐林; 王雪; 赵姜维
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2019-05-21
Filing date: 2019-05-21
Publication date: 2023-05-09
Anticipated expiration: 2039-05-21
Also published as: CN111978446A

Abstract

The invention discloses polybutadiene rubber, a preparation method thereof, and aromatic vinyl resin using the polybutadiene rubber as a toughening agent and a preparation method thereof. The polybutadiene rubber according to the present invention has a molecular weight of four-peak distribution and is prepared by polymerizing 1, 3-butadiene in an organic solvent in the presence of an organolithium initiator and a structure regulator, and contacting the resulting polymerization solution with a coupling agent having a molar amount of n to effect a coupling reaction, wherein the coupling agent is a tetrafunctional coupling agent _C The molar amount of the organolithium initiator is n _I ，2.8n _I ≥(n _C ×4)≥1.4n _I . The preparation method obtains the polybutadiene rubber with four-peak distribution through one-step coupling reaction, and the polybutadiene rubber is used as a toughening agent of the aromatic vinyl resin, so that the impact resistance of the aromatic vinyl resin can be obviously improved, and meanwhile, the good glossiness can be maintained.

Description

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

Technical Field

The invention relates to polybutadiene rubber and a preparation method and application thereof, and also relates to aromatic vinyl resin using the 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 polybutadiene rubber and a preparation method thereof.

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, a high molecular weight component having a number average molecular weight of 280,000-470,000, a second intermediate molecular weight component having a number average molecular weight of 210,000-370,000, a first intermediate molecular weight component having a number average molecular weight of 150,000-250,000, a low molecular weight component having a number average molecular weight of 80,000 to 120,000, the high molecular weight component being present in an amount of 1 to 30% by weight, the second intermediate molecular weight component being present in an amount of 10 to 45% by weight, the first intermediate molecular weight component being present in an amount of 20 to 40% by weight, and the low molecular weight component being present in an amount of 5 to 55% by weight, 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 polybutadiene rubber, which comprises the steps of:

(1) Polymerizing 1, 3-butadiene in an organic solvent under anionic polymerization conditions in the presence of an organolithium initiator and a structure regulator to obtain a polymerization solution containing polybutadiene, wherein the organolithium initiator is used in an amount such that the polybutadiene has a number average molecular weight of 80,000-120,000;

(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 tetrafunctional coupling agents, and the molar weight of the coupling agent is n _C The molar amount of the organolithium initiator is n _I ，2.8n _I ≥(n _C ×4)＞1.4n _I 。

According to a third aspect of the present invention, there is provided a 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 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 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 polybutadiene rubber according to 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 in a multi-stage distribution, and when used as a toughening agent for an aromatic vinyl resin, the components of the stages cooperate with each other so that the aromatic vinyl resin has a significantly improved impact resistance, while also maintaining a higher gloss of the aromatic vinyl resin.

According to the preparation method of the polybutadiene rubber, the 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 four functionalities is adopted, the coupling agent with four functionalities is excessive relative to the organolithium 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 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 polybutadiene rubber containing a coupling center atom and having a molecular weight in a four-peak distribution, a high molecular weight componentNumber average molecular weight (M) _n ) 280,000-470,000, preferably 300,000-450,000, more preferably 320,000-430,000; the second intermediate molecular weight component has a number average molecular weight of 210,000-370,000, preferably 230,000-360,000, more preferably 240,000-340,000; the first intermediate molecular weight component has a number average molecular weight of 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 to 120,000, preferably 85,000 to 115,000, more preferably 90,000 to 110,000. The polybutadiene rubber according to the present invention has a number average molecular weight size relationship of the high molecular weight component, the second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component as follows: the high molecular weight component has a number average molecular weight > the second intermediate molecular weight component has a number average molecular weight > the first intermediate molecular weight component has a number average molecular weight > the low molecular weight component.

According to the 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 second intermediate molecular weight component may have a molecular weight distribution index of from 1 to 1.1, preferably from 1.02 to 1.08; the first intermediate molecular weight component may have a molecular weight distribution index of from 1 to 1.1, preferably from 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 polybutadiene rubber according to the present invention has a high molecular weight component content 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 10 to 45 wt%, preferably 12 to 42 wt%, more preferably 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 low molecular weight component is present in an amount of 5 to 55 wt.%, preferably 8 to 40 wt.%, more preferably 10 to 30 wt.%.

According to the polybutadiene rubber of the present invention, the number average molecular weight of the polybutadiene rubber may be 150,000-250,000, preferably 170,000-240,000, more preferably 180,000-220,000. According to the polybutadiene rubber of the present invention, the molecular weight distribution index of the polybutadiene rubber may be 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 refer to the overall number average molecular weight and the overall molecular weight distribution index of the polybutadiene rubber.

In the invention, the number average molecular weight and the molecular weight distribution index are determined by adopting a gel permeation chromatography, and the mass percentages 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 determined 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 second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component is calculated by the following method:

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 second intermediate molecular weight component+the peak area corresponding to the first intermediate molecular weight component+the peak area corresponding to the low molecular weight component) in the GPC curve;

The mass percent (%) of the second intermediate molecular weight component=the peak area of the peak corresponding to the second intermediate molecular weight component/(the peak area corresponding to the high molecular weight component+the peak area corresponding to the second intermediate molecular weight component+the peak area corresponding to the first intermediate molecular weight component+the peak area corresponding to the low molecular weight component) in the GPC curve;

the mass percent (%) of the first intermediate molecular weight component=the peak area of the peak corresponding to the first intermediate molecular weight component/(the peak area corresponding to the high molecular weight component+the peak area corresponding to the second intermediate molecular weight component+the peak area corresponding to the first intermediate molecular weight component+the peak area corresponding to the low molecular weight component) in the 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 second intermediate molecular weight component+the peak area corresponding to the first intermediate 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 peak area obtained by GPC test.

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 to 200cP, more preferably 120 to 180cP, still more preferably 130 to 170cP.

The polybutadiene rubber according to the present invention has a reduced viscosity of a 5 wt.% styrene solution at 25℃and thus better processability than 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. According to the polybutadiene rubber of the present invention, the viscosity of the polybutadiene rubber in a 5 wt.% styrene solution at 25℃is X centipoise, the viscosity of the low molecular weight component in the polybutadiene rubber in a 5 wt.% styrene solution at 25℃is Y centipoise, 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 1.2-1.5, more preferably 1.25-1.4. A linear polybutadiene rubber having a molecular weight corresponding to the high molecular weight component, a linear polybutadiene rubber having a molecular weight corresponding to the second intermediate component, a linear polybutadiene rubber having a molecular weight corresponding to the first intermediate component and a ratio of a viscosity to Y in a 5 wt% styrene solution at 25 ℃ of a compound obtained by compounding a linear polybutadiene rubber having a component corresponding to a low molecular weight is usually 4 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.

According to the polybutadiene rubber of the present invention, the Mooney viscosity of the polybutadiene rubber at 100℃may be 70 to 80, preferably 45 to 75, more preferably 50 to 70, still more preferably 55 to 60.

In the invention, the Mooney viscosity is measured by an SMV-201 SK-160 Mooney viscometer manufactured by Shimadzu corporation according to a method specified in Chinese national standard GB/T1232-92, and the test conditions comprise: ML (1+4), the test temperature is 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 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 formed by 1, 2-polymerization of 1, 3-butadiene, and 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 polybutadiene rubber of the present invention, the polybutadiene rubber contains a coupling center atom. The coupling center atom may be to be derived from the coupling agent. Preferably, the coupling center atoms are 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 coupling 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, and are components formed by reacting a coupling agent with the reactive end groups of the corresponding linear polymers, and connecting 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, 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, or 230ppm, preferably 105 to 190ppm, more preferably 110 to 180ppm, and even more preferably 115 to 175ppm.

According to the polybutadiene rubber disclosed by the invention, the coupling agent is one or more than two of tetrafunctional coupling agents. Specific examples of the coupling center atoms 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 coupling center atoms contained in the molecular chains of the high molecular weight component, the second intermediate molecular weight component and the first intermediate molecular weight component, 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 bonded to only one polymer chain. According to the polybutadiene rubber of the present invention, the molar percentage of coupling center atoms in the polybutadiene rubber is N _Z The mole percent of the high molecular weight component is N _H The second intermediate molecular weight component has a mole percent of N _M1 First intermediate molecular weight groupThe mole percentage of the components is N _M2 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 second intermediate molecular weight component has a coupling arm number A _M1 The first intermediate molecular weight component has a coupling arm number A _M2 ，4(N _H +N _M1 +N _M2 +N _L )≥(N _Z ×4)≥(N _H ×A _H +N _M1 ×A _M1 +N _M2 ×A _M2 +N _L )。(N _Z ×4)/(N _H ×A _H +N _M1 ×A _M1 +N _M2 ×A _M2 +N _L ) Preferably 1-3, 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 1.3-2.8, still more preferably 1.4-2.2.

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 percentages and the number of coupling arms 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 determined by GPC, 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 the second intermediate molecular weight component = number average molecular weight of the second intermediate molecular weight component/number average molecular weight of the low molecular weight component;

number of coupling arms of the first intermediate molecular weight component = number average molecular weight of the first intermediate molecular weight component/number average molecular weight of the 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 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);

The 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);

the mole percent of the first 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 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 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 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 invention may also 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 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 polybutadiene rubber may be 0.1 to 0.4:100.

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 I,

R ₁ li (I)

In the formula I, R ₁ Is C ₁ -C ₆ Alkyl, C of (2) ₃ -C ₁₂ Cycloalkyl, C ₇ -C ₁₄ Aralkyl of (a) or C ₆ -C ₁₂ A kind of electronic device aryl groups.

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 (a) 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 process of the present invention, in a preferred embodiment, in step (1), the organolithium initiator is used in such an amount that the polybutadiene has a number average molecular weight of 85,000 to 115,000, preferably 90,000 to 110,000. According to this preferred embodiment, the molar ratio of 1, 3-butadiene to the organolithium initiator may be in the range 1400-2300:1, preferably 1500-2200:1, more preferably 1600-2000:1. 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 tetrahydrofuran, tetrahydrofurfuryl alkylOne or more of ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether and diethylene glycol dialkyl ether, wherein the alkyl group can 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-adjusting agent is preferably one or two 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 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-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 0.04 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 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 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 ，2.8n _I ≥(n _C ×4)≥1.4n _I . According to the preparation method provided by the invention, the polybutadiene rubber with different molecular weights can be obtained through one-step coupling reaction by adopting excessive coupling agent, so that more than two coupling agents are avoided or the polybutadiene rubber with different molecular weights is compounded. Preferably n _C /n _I The ratio of (2) is 0.37-0.65:1, 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 0.37-0.5:1. further preferably, n _C /n _I The ratio of (2) is 0.4-0.45:1.

in the step (2), the coupling agent is one or more than two 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.

In 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 0.1 to 1MPa, preferably 0.2 to 0.5MPa, the pressure being gauge pressure.

In step (2), the coupling agent is used in an amount such that the coupled polymer comprises 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 second intermediate molecular weight component has a number average molecular weight of 210,000-370,000, preferably 230,000-360,000, more preferably 240,000-340,000; the first intermediate molecular weight component has a number average molecular weight of 150,000-250,000, preferably 160,000-240,000, more preferably 170,000-230,000; 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 high molecular weight component is contained 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 10 to 45 wt%, preferably 12 to 42 wt%, more preferably 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 low molecular weight component is present in an amount of 5 to 55 wt.%, preferably 8 to 40 wt.%, more preferably 10 to 30 wt.%.

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, zn) in a polymerization system to be separated from the 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): and (3) adding at least one auxiliary agent into the termination reaction liquid obtained in the step (3) to endow the finally prepared polybutadiene rubber with new properties and/or improve the properties of the finally prepared 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 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 stripped to remove the solvent therefrom, thereby obtaining 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-butadiene rubber produced by the production 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 obtain the molecular weight four-peak distribution 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 by controlling the dosage of the coupling agent to be excessive without compounding.

The polybutadiene rubber according to the present invention can be added to an aromatic vinyl resin as a toughening agent by conventional methods, for example: polybutadiene rubber may be added during polymerization to form an aromatic vinyl resin, or may be added as a toughening agent to the aromatic vinyl resin.

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 polybutadiene rubber as 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 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 is 100-170℃and the time is 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 16kJ/m ² Above (e.g. 16-25 kJ/m) ² ) Typically 17kJ/m ² Above, e.g. 18-22kJ/m ² The method comprises the steps of carrying out a first treatment on the surface of the The 60 ° surface gloss may be 55 or more, typically 60 or more, e.g., 65-75.

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 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 Inoki reagent company, tetrahydrofurfuryl ethyl ether was purchased from Balanwei reagent company, silicon tetrachloride and methyltrichlorosilane were purchased from Balanwei reagent company (analytically pure, diluted to a concentration of 0.1 mol/L), and n-butyllithium and sec-butyllithium were purchased from Balanwei reagent company, diluted with hexane 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 excess of a tetrafunctional coupling agent (specific kinds and amounts are listed in Table 2), and a 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 polybutadiene rubber. The resulting polymerization solution was subjected to steam coagulation desolventizing treatment and dried to obtain polybutadiene rubber, the structure and property parameters of which are shown in tables 3 and 4.

Examples 2 to 9

Polybutadiene rubber was prepared by the same procedures as in example 1, except that the conditions shown in tables 1 and 2 were employed, respectively, to obtain polybutadiene rubbers, and the structure and property parameters of the obtained polybutadiene rubbers are shown in tables 3 and 4.

Comparative example 1

A polybutadiene rubber was prepared by the same procedures as in example 1, except that in step (2), the amount of the coupling agent was as shown in Table 2, and the structure and property parameters of the obtained polybutadiene rubber were as shown in tables 3 and 4.

Comparative example 2

Comparative example 3

Polybutadiene rubber was prepared by the same procedures 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 resulting polybutadiene rubber are set forth in tables 3 and 4.

Comparative example 4

A 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 tetrachlorosilane in step (2) was 3.4mmol. The structural and property parameters of the resulting polybutadiene rubber are set forth in tables 3 and 4.

Comparative example 5

Low cis-polybutadiene linear polymers having number average molecular weights of 9.2 tens of thousands, 18.5 tens of thousands, 26.2 tens of thousands and 35.4 tens of thousands were prepared by the same procedures as in the steps (1) and (3) of example 1 (see Table 1 and Table 3 for specific reaction conditions), and the four linear polymers were mixed in a mass ratio of 9.2 tens of thousands/18.5 tens of thousands/26.2 tens of thousands/35.4 tens of thousands=0.98/2.1/2.28/1 to obtain polybutadiene rubber linear copolymers, the structure and property parameters of which are shown in tables 3 and 4.

TABLE 1

TABLE 2

TABLE 3 Table 3

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 peak corresponding to 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 Table 4

¹ : X/Y, X is the viscosity of the polybutadiene rubber prepared in this example or comparative example in a 5 wt.% styrene solution at 25℃and Y is the viscosity of the polybutadiene rubber prepared in this example or comparative exampleThe low molecular weight component of the polybutadiene rubber prepared in proportion has a viscosity at 25℃in a 5% by weight styrene solution.

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 _M1 Number average molecular weight of second intermediate molecular weight component/number average molecular weight of low molecular weight component;

A _M2 number average molecular weight of first intermediate 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 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);

N _M1 = (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);

N _M2 = (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 + number average molecular weight of the first intermediate molecular weight component corresponds to the low molecular weight component)Number average molecular weight of the 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 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, in the polybutadiene rubber according to the present invention, the content of 4 times the coupling center atoms is compared with (N) _H ×A _H +N _M1 ×A _M1 +N _M2 ×A _M2 +N _L ) The ratio of 1 or more indicates that in the 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, the second intermediate-molecular-weight component and the first intermediate-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 from a comparison of example 1 with comparative example 5, the low cis-polybutadiene rubber according to the present invention has a reduced viscosity as compared with a mixture obtained by mixing four linear polymers, and thus, has better processability. 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 to 9 the high impact polystyrene resin was prepared by using the polybutadiene rubber prepared in examples 1 to 9 as a toughening agent and adopting a conventional bulk method, wherein the proportion of the toughening agent relative to the styrene monomer was 8%, and the high impact polystyrene was obtained by the specific polymerization method:

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

TABLE 6

Numbering device	Notched Izod impact Strength (kJ/m) ² )	Surface glossiness (60 o)
			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
Experiment comparative example 1	15.6	58
			Experiment comparative example 2	7.8	65
Experiment comparative example 3	13.8	64
			Experiment comparative example 4	12.6	73
Experiment comparative example 5	17.4	34
			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 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 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

1. A polybutadiene rubber containing a coupling center atom, and having a molecular weight of four peak distribution, a high molecular weight component having a number average molecular weight of 280,000-470,000, a second intermediate molecular weight component having a number average molecular weight of 210,000-370,000, a first intermediate molecular weight component having a number average molecular weight of 150,000-250,000, a low molecular weight component having a number average molecular weight of 80,000 to 120,000, a content of the high molecular weight component of 1 to 30% by weight, a content of the second intermediate molecular weight component of 10 to 45% by weight, a content of the first intermediate molecular weight component of 20 to 40% by weight, a content of the low molecular weight component of 5 to 55% by weight, and a number average molecular weight size relationship of the high molecular weight component, the second intermediate molecular weight component, the first intermediate molecular weight component and the low molecular weight component being: the high molecular weight component has a number average molecular weight > the second intermediate molecular weight component has a number average molecular weight > the first intermediate molecular weight component has a number average molecular weight > the low molecular weight component.

2. The polybutadiene rubber according to claim 1, wherein the high molecular weight component has a number average molecular weight of 300,000-450,000, the second intermediate molecular weight component has a number average molecular weight of 230,000-360,000, the first intermediate 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 polybutadiene rubber according to claim 1, wherein the high molecular weight component has a number average molecular weight of 320,000-430,000, the second intermediate molecular weight component has a number average molecular weight of 240,000-340,000, the first intermediate 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 polybutadiene rubber according to any of claims 1 to 3, wherein 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.

5. The polybutadiene rubber according to claim 1 to 3, wherein the content of the high molecular weight component is 4 to 25% by weight, the content of the second intermediate molecular weight component is 12 to 42% by weight, the content of the first intermediate molecular weight component is 25 to 40% by weight and the content of the low molecular weight component is 8 to 40% by weight, based on the total amount of the polybutadiene rubber.

6. The polybutadiene rubber according to claim 1 to 3, wherein the content of the high molecular weight component is 8 to 22% by weight, the content of the second intermediate molecular weight component is 25 to 40% by weight, the content of the first intermediate molecular weight component is 26 to 38% by weight and the content of the low molecular weight component is 10 to 30% by weight, based on the total amount of the polybutadiene rubber.

7. The polybutadiene rubber according to claim 1, wherein the polybutadiene rubber has a number average molecular weight of 150,000-250,000.

8. The polybutadiene rubber according to claim 1, wherein the polybutadiene rubber has a number average molecular weight of 170,000-240,000.

9. The polybutadiene rubber according to claim 1, wherein the polybutadiene rubber has a number average molecular weight of 180,000-220,000.

10. The polybutadiene rubber according to any of claims 1 and 7 to 9, wherein the molecular weight distribution index of the polybutadiene rubber is 1.5 to 2.5.

11. The polybutadiene rubber according to claim 1, wherein the viscosity of the polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is above 90 cP.

12. The polybutadiene rubber according to claim 1, wherein the viscosity of the polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is 100-200cP.

13. The polybutadiene rubber according to claim 1, wherein the viscosity of the polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is 120-180cP.

14. The polybutadiene rubber according to any of claims 1 and 11 to 13, wherein the viscosity of the polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is X centipoise, the viscosity of the low molecular weight component in the polybutadiene rubber in a 5 wt.% styrene solution at 25 ℃ is Y centipoise, and the ratio of X/Y is 1 to 1.6.

15. The polybutadiene rubber according to claim 1 and 11 to 13, wherein the viscosity of the polybutadiene rubber in a 5 wt.% styrene solution at 25℃is X centipoise, the low molecular weight component of the polybutadiene rubber has a viscosity of Y centipoise in a 5 wt.% styrene solution at 25℃and a ratio of X/Y of 1.2 to 1.5.

16. The polybutadiene rubber according to claim 1, wherein the Mooney viscosity of the polybutadiene rubber at 100℃is 70-80.

17. The polybutadiene rubber according to claim 1, wherein the mooney viscosity of the polybutadiene rubber at 100 ℃ is 45-75.

18. The polybutadiene rubber according to claim 1, wherein the Mooney viscosity of the polybutadiene rubber at 100℃is 50-70.

19. The polybutadiene rubber according to claim 1, wherein the vinyl content of the polybutadiene rubber is 8-20 wt%.

20. The polybutadiene rubber according to claim 1, wherein the vinyl content of the polybutadiene rubber is 10-16 wt%.

21. The polybutadiene rubber according to claim 1, wherein the content of cis 1, 4-structural units of the polybutadiene rubber is 30-40 wt%.

22. The polybutadiene rubber according to any of claims 1 to 3, 7 to 9, 11 to 13 and 16 to 21, wherein said high molecular weight component, said second intermediate molecular weight component and said first intermediate molecular weight component contain coupling central atoms, at least part of said low molecular weight component contains coupling central atoms, said low molecular weight component being a linear polymer.

23. Polybutadiene rubber according to claim 22, wherein said coupling central atom is silicon and/or tin.

24. Polybutadiene rubber according to claim 22, wherein the mass content of the coupling central atoms is from 85 to 230ppm, based on the total amount of polybutadiene rubber.

25. Polybutadiene rubber according to claim 22, wherein the mass content of the coupling central atoms is 100 to 200ppm, based on the total amount of polybutadiene rubber.

26. Polybutadiene rubber according to claim 22, wherein the mass content of the coupling central atoms is 105 to 190ppm, based on the total amount of polybutadiene rubber.

27. The polybutadiene rubber of claim 22, wherein the coupling center atom is derived from a coupling agent.

28. The polybutadiene rubber according to claim 27, wherein said coupling agent is one or more than two of tetrafunctional coupling agents.

29. Polybutadiene rubber according to claim 27, wherein the coupling agent is tetrachlorosilane and/or tin tetrachloride.

30. The polybutadiene rubber of claim 27, wherein the polybutadiene rubber has a mole percent of coupling center atoms of N _Z The mole percent of the high molecular weight component is N _H The second intermediate molecular weight component has a mole percent of N _M1 The mole percent of the first intermediate molecular weight component is N _M2 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 second intermediate molecular weight component has a coupling arm number A _M1 The first intermediate molecular weight component has a coupling arm number A _M2 ，4(N _H +N _M1 +N _M2 +N _L )≥(N _Z ×4)≥(N _H ×A _H +N _M1 ×A _M1 +N _M2 ×A _M2 +N _L )。

31. The polybutadiene rubber according to claim 30, wherein (N) _Z ×4)/(N _H ×A _H +N _M1 ×A _M1 +N _M2 ×A _M2 +N _L ) The ratio of (2) is 1-3.

32. The polybutadiene rubber according to claim 30, wherein (N) _Z ×4)/(N _H ×A _H +N _M1 ×A _M1 +N _M2 ×A _M2 +N _L ) The ratio of (2) is 1.3-2.8.

33. The polybutadiene rubber according to claim 30, wherein (N) _Z ×4)/(N _H ×A _H +N _M1 ×A _M1 +N _M2 ×A _M2 +N _L ) The ratio of (2) is 1.4-2.2.

34. A process for preparing the polybutadiene rubber according to claim 1, which comprises the following steps:

(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 tetrafunctional coupling agents, and the molar weight of the coupling agent is n _C The molar amount of the organolithium initiator is n _I ，2.8n _I ≥(n _C ×4)≥1.4n _I 。

35. The method according to claim 34, wherein in the step (2), n _C /n _I The ratio of (2) is 0.37-0.65:1.

36. the method according to claim 34, wherein in the step (2), n _C /n _I The ratio of (2) is 0.37-0.5:1.

37. the method according to claim 34, wherein in the step (2), n _C /n _I The ratio of (2) is 0.4-0.45:1.

38. the production process according to any one of claims 34 to 37, wherein in the step (2), the coupling agent is used in such an amount that the coupled polymer contains a high molecular weight component having a number average molecular weight of 280,000-470,000, a second intermediate molecular weight component having a number average molecular weight of 210,000-370,000, a first intermediate 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 content of the high molecular weight component being 1 to 30% by weight, the content of the second intermediate molecular weight component being 10 to 45% by weight, the content of the first intermediate molecular weight component being 20 to 40% by weight, and the content of the low molecular weight component being 5 to 55% by weight based on the total amount of the polybutadiene rubber.

39. The production process according to any one of claims 34 to 37, wherein in the step (2), the coupling agent is used in such an amount that the coupled polymer contains a high molecular weight component having a number average molecular weight of 300,000-450,000, a second intermediate molecular weight component having a number average molecular weight of 230,000-360,000, a first intermediate molecular weight component having a number average molecular weight of 160,000-240,000, and a low molecular weight component having a number average molecular weight of 85,000 to 115,000, the high molecular weight component being in an amount of 4 to 25% by weight, the second intermediate molecular weight component being in an amount of 12 to 42% by weight, the first intermediate molecular weight component being in an amount of 25 to 40% by weight, and the low molecular weight component being in an amount of 8 to 40% by weight, based on the total amount of the polybutadiene rubber.

40. The production process according to any one of claims 34 to 37, wherein in the step (2), the coupling agent is used in such an amount that the coupled polymer contains a high molecular weight component having a number average molecular weight of 320,000-430,000, a second intermediate molecular weight component having a number average molecular weight of 240,000-340,000, a first intermediate molecular weight component having a number average molecular weight of 170,000-230,000, and a low molecular weight component having a number average molecular weight of 90,000 to 110,000, the high molecular weight component being 8 to 22% by weight, the second intermediate molecular weight component being 25 to 40% by weight, the first intermediate molecular weight component being 26 to 38% by weight, and the low molecular weight component being 10 to 30% by weight, based on the total amount of the polybutadiene rubber.

41. The production process according to claim 34, 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.

42. The process according to claim 34 or 41, wherein the coupling agent is one or more of tetrafunctional coupling agents.

43. The method according to claim 34 or 41, wherein the coupling agent is a silicon-containing coupling agent and/or a tin-containing coupling agent.

44. The process according to claim 34 or 41, wherein the coupling agent is tetrachlorosilane and/or tin tetrachloride.

45. The process according to claim 34, wherein the organolithium initiator is a compound of formula I,

R ₁ li (I)

In the formula I, R ₁ 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).

46. The process of claim 34, 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.

47. The process according to claim 34, wherein in step (1), the organolithium initiator is used in such an amount that the polybutadiene has a number average molecular weight of 85,000 to 115,000.

48. The process according to claim 34, wherein in step (1), the organolithium initiator is used in such an amount that the polybutadiene has a number average molecular weight of 90,000 to 110,000.

49. The process according to any one of claims 34 and 45 to 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 34 and 45-48, wherein in step (1), the molar ratio of 1, 3-butadiene to organolithium initiator is from 1500 to 2200:1.

51. the process of any one of claims 34 and 45-48, wherein in step (1), the molar ratio of 1, 3-butadiene to organolithium initiator is 1600-2000:1.

52. the production method according to claim 34, wherein the structure-adjusting agent is one or more of an ether-type structure-adjusting agent and an amine-type structure-adjusting agent.

53. The method according to claim 34, wherein the structure-controlling agent is one or more of tetrahydrofuran, tetrahydrofurfuryl alkyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether and diethylene glycol dialkyl ether.

54. The process of claim 53 wherein said alkyl is C ₁ -C ₄ An alkyl group.

55. The process according to claim 34, wherein, the structure regulator is one or more than two 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.

56. The method according to claim 34, wherein the structure-adjusting agent is one or more of tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether and tetrahydrofurfuryl propyl ether.

57. The process of any one of claims 34 and 52-56, wherein in step (1), the molar ratio of the structure modifier to the organolithium initiator is from 0.01 to 1:1.

58. the process according to claim 34, wherein in the step (1), the polymerization is carried out at a temperature of 0 to 100 ℃, the duration of the polymerization is 20-80 minutes, the polymerization is carried out at a pressure of 0.1-1MPa, and the pressure is gauge pressure.

59. The production method according to claim 34, wherein in the step (1), the polymerization is performed at a temperature of 40 to 90 ℃, the duration of the polymerization is 30 to 60 minutes, and the polymerization is performed at a pressure of 0.2 to 0.5MPa, the pressure being a gauge pressure.

60. The method of claim 34, further comprising the step (3) of contacting the coupled polymer solution with a terminating agent to effect a termination reaction.

61. The process of claim 60, wherein the terminator is C ₁ -C ₄ One or more of alcohol, organic acid and carbon dioxide.

62. The process of claim 60, wherein the terminator is one or more of isopropanol, stearic acid, citric acid and carbon dioxide.

63. Use of the polybutadiene rubber of any of claims 1-33 as an aromatic vinyl resin toughening agent.

64. An aromatic vinyl resin comprising an aromatic vinyl matrix resin and a toughening agent, wherein the toughening agent is the polybutadiene rubber of any one of claims 1 to 33.

65. 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 polybutadiene rubber of any of claims 1 to 33.