Butadiene polymer as well as preparation method and application thereof

Abstract

The invention provides a butadiene polymer as well as a preparation method and application thereof. The butadiene polymer is prepared from the following raw materials: a monomer and an initiator, the monomers comprise the following components in parts by weight: 75-100 parts of butadiene, 0-12.5 parts of an aromatic vinyl monomer and 0-12.5 parts of an alkenyl cyanide monomer; the initiator comprises a first initiator and / or a second initiator; the first initiator comprises an oil-soluble initiator and a water-soluble initiator; the second initiator comprises a redox initiator; the mass percentage content of a 1, 2-butadiene structural unit in the molecular structure of the butadiene polymer is less than or equal to 30%. According to the present invention, the ABS resin prepared from the butadiene polymer has characteristics of long oxidation induction time, small color value change before and after heat treatment, and excellent heat resistance and excellent weather resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a butadiene-based polymer, a preparation method thereof, and an application thereof. Background Art

[0002] ABS resin is a terpolymer of acrylonitrile (A), butadiene (B), and styrene (S), and has the common properties of the three components; among them, the acrylonitrile structural unit improves the chemical stability and heat resistance of the material; the benzene ring structure in the styrene molecule has high rigidity, which increases the regularity of the molecular chain, is beneficial to the processing and forming of the material, and can improve the surface hardness and gloss of the material; while butadiene endows the material with better impact resistance, making ABS resin applicable to industries such as automobiles, electronics, and electrical appliances.

[0003] The structure of ABS resin consists of a continuous phase and a dispersed phase. Among them, styrene-acrylonitrile copolymer serves as the continuous phase, and the dispersed polybutadiene rubber phase serves as the dispersed phase and is distributed in the continuous phase to form a "sea-island structure". This "sea-island structure" is an important reason for the excellent comprehensive properties of ABS plastics. However, it is precisely this structure that causes certain drawbacks of ABS resin. Since polybutadiene rubber includes vinyl structures (1,2-butadiene structural units), Trans-1,4 structures (trans-1,4-butadiene structural units), and Cis-1,4 structures (cis-1,4-butadiene structural units). The existence of 1,2-butadiene structural units affects the weather resistance and heat resistance of the material; not only makes the butadiene-based polymer prone to polymer degradation, branching, and cross-linking reactions during subsequent processing (such as in a twin-screw extruder), but also makes the material prone to problems such as aging and color change during long-term use.

[0004] Therefore, developing a butadiene-based polymer that can improve the heat resistance and weather resistance of ABS resin is an urgent problem to be solved in this field. Summary of the Invention

[0005] Aiming at the deficiencies existing in the prior art, the purpose of the present invention is to provide a butadiene-based polymer, a preparation method thereof, and an application thereof. It solves the problems in the prior art that the butadiene-based latex has poor thermal stability, is prone to degradation, branching, and cross-linking, and the color difference of the material containing it changes greatly before and after heat treatment, and the weather resistance is poor.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a butadiene-based polymer, wherein the raw materials for preparing the butadiene-based polymer include monomers and initiators; in parts by weight, the monomers include 75 to 100 parts of butadiene, 0 to 12.5 parts of aromatic vinyl monomers and 0 to 12.5 parts of alkenyl cyanide monomers; the initiator includes a first initiator and / or a second initiator; the first initiator includes an oil-soluble initiator and a water-soluble initiator; the second initiator includes a redox initiator; and the mass percentage of 1,2-butadiene structural units in the molecular structure of the butadiene-based polymer is ≤30%.

[0008] In the present invention, an initiator of a specific composition is selected, and the content of 1,2-butadiene structural units in the molecular structure of the butadiene polymer is controlled within a specific range, which can reduce the degradation, branching and cross-linking of the butadiene polymer, improve the heat resistance and weather resistance of the butadiene polymer, and make the ABS resin material including the butadiene polymer have a long oxidation induction time and a small color value change before and after heat treatment.

[0009] In the present invention, the monomers include 75 to 100 parts of butadiene (for example, 75, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100 or any range between the above values, preferably 85 to 100 parts), 0 to 12.5 parts of aromatic vinyl monomer (for example, 0, 0.5, 1, 2, 4, 6, 8, 10, 12, 12.5 or any range between the above values, preferably 0 to 8 parts) and 0 to 12.5 parts of alkenyl cyanide monomer (for example, 0, 0.5, 1, 2, 4, 6, 8, 10, 12, 12.5 or any range between the above values, preferably 0 to 5 parts).

[0010] In the present invention, the aromatic vinyl monomer includes but is not limited to at least one of styrene, α-methylstyrene and 2-methylstyrene; the vinyl cyanide monomer includes but is not limited to acrylonitrile and / or methacrylonitrile.

[0011] In the present invention, other monomers may be added according to actual needs, including but not limited to (meth) alkyl acrylate monomers.

[0012] In the present invention, the mass percentage content of 1,2-butadiene structural units in the molecular structure of the butadiene-based polymer is ≤ 30%, and for example, it can be 1%, 2%, 4%, 5%, 6%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% or the range between any of the above values.

[0013] Preferably, the mass percentage content of 1,2-butadiene structural units in the molecular structure of the butadiene-based polymer is ≤ 20%, and more preferably, the mass percentage content of 1,2-butadiene structural units is 5 - 15%.

[0014] In the present invention, since the butadiene-based polymer is subsequently used to prepare ABS resin, it is necessary to ensure that it has high reactivity. Therefore, more preferably, the mass percentage content of 1,2-butadiene structural units is greater than 5%; if the mass percentage content of 1,2-butadiene structural units is too low, the reactivity is low, which affects its reactivity with aromatic vinyl monomers and vinyl cyanide monomers, and further affects the comprehensive properties of the obtained ABS material.

[0015] Preferably, the molecular structure of the butadiene-based polymer further includes trans-1,4-butadiene structural units and cis-1,4-butadiene structural units.

[0016] Preferably, the mass percentage content of trans-1,4-butadiene structural units in the butadiene-based polymer is 30 - 60%, and for example, it can be 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60% or the range between any of the above values; more preferably, the mass percentage content of trans-1,4-butadiene structural units is 40 - 55%, and particularly preferably, the mass percentage content of trans-1,4-butadiene structural units is 45 - 53%.

[0017] Preferably, the mass percentage content of cis-1,4-butadiene structural units in the butadiene-based polymer is 20 - 50%, and for example, it can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50% or the range between any of the above values; more preferably, the mass percentage content of cis-1,4-butadiene structural units is 35 - 45%.

[0018] Preferably, based on 100 parts by mass of the solid of the monomer, the mass of the initiator is 0.01 to 8 parts, for example, it can be 0.01 part, 0.02 part, 0.04 part, 0.06 part, 0.08 part, 0.1 part, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 2 part, 3 part, 4 part, 5 part, 6 part, 7 part, 8 part or the range between any of the above values; more preferably, the mass of the initiator is 0.1 to 7 parts.

[0019] Preferably, the mass content of the initiator and the 1,2-butadiene structural unit in the butadiene-based polymer satisfies the following relationship.

[0020] I = I 1 +I 2 15 ≤ V ≤ 30%, and / or, I = I 2 ′+I 3 5 ≤ V < 15%.

[0021] Wherein, I 1 = 100×130 lg(V / 4) ; I 2 = 100×130 ln(1.5V) ; I 3 = 100×130 lgV ; I 2 ′ = 100I 2 .

[0022] Wherein, V is the theoretical mass content of the 1,2-butadiene structural unit in the butadiene-based polymer; I is the total mass of the initiator; I 1 is the mass of the water-soluble initiator; I 2 is the mass of the oil-soluble initiator; I 3 is the mass of the reducing agent in the redox initiator.

[0023] In the present invention, the theoretical content of the 1,2-butadiene structural unit in the butadiene-based polymer is the content of the target 1,2-butadiene structural unit, that is, if it is desired to obtain a butadiene-based polymer with a 1,2-butadiene structural unit content of 15%, then V in the formula is 15%.

[0024] In the present invention, when a butadiene-based polymer with a V content of 15-30% is obtained, a composite initiator system composed of an oil-soluble initiator and a water-soluble initiator is used. When a butadiene-based polymer with a V content of 5-15% is obtained, an oxidation-reduction system composed of an oil-soluble initiator and a reducing agent is used. By the relationship between V and the composition and content of the initiator in the formula, the initiator system is regulated so that the actual mass content of the 1,2-butadiene structural unit in the polybutadiene polymer matches the designed mass content, the stereoregularity of the butadiene-based polymer is adjusted, the 1,4-addition ratio of butadiene monomer is increased, the content of the 1,2-butadiene structural unit in the butadiene-based polymer is controlled within a specific range, a butadiene-based polymer with a target structure is obtained, thereby reducing the degradation, branching and cross-linking of the butadiene-based polymer in the subsequent processing process, improving the heat resistance and weather resistance of the butadiene-based polymer, making the oxidation induction time of the ABS resin material including the butadiene-based polymer long and the color value change small before and after heat treatment; at the same time, ensuring that the butadiene-based polymer has high reaction activity and obtaining an ABS resin with better performance.

[0025] In the present invention, within the range of V≤30%, a suitable initiator system can be selected according to actual needs to obtain the required butadiene-based polymer; for example, on the premise of ensuring that the butadiene polymer has certain reaction activity, if an ABS resin with better heat resistance and weather resistance is desired, preferably formula I = I 2 ′+I 3 , 5≤V<15%; if an ABS resin with better heat resistance and weather resistance is desired and other properties need to be considered at the same time, and a butadiene-based polymer with high reaction activity is required, then preferably formula I = I 1 +I 2 , 15≤V≤30%.

[0026] Preferably, the oil-soluble initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, benzoyl peroxide or bis(2-ethylhexyl) peroxydicarbonate.

[0027] Preferably, the water-soluble initiator includes at least one of potassium persulfate, ammonium persulfate, hydrogen peroxide, sodium persulfate, azobisisobutylamidine hydrochloride, azobisisobutimidazoline hydrochloride, azodicyanovaleric acid or azodiisopropylimidazoline.

[0028] Preferably, the oxidant in the redox initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, benzoyl peroxide or bis(2-ethylhexyl) peroxydicarbonate.

[0029] Preferably, the reducing agent in the redox initiator includes at least one of ferrous sulfate, ferric chloride, sodium formaldehyde sulfoxylate, sodium metabisulfite or tetraethyl pentanediamine.

[0030] Preferably, when the initiator is selected from redox initiators, the preparation raw materials further include a metal complexing agent and a co-reducing agent.

[0031] Preferably, the mass ratio of the reducing agent, the metal complexing agent and the co-reducing agent is 1:(3 - 7):(0.5 - 3.5), wherein the specific value in (3 - 7) can be, for example, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.2, 6.4, 6.6, 6.8, 7 or the range between any of the above values; the specific value in (0.5 - 3.5) can be, for example, 0.5, 0.6, 0.8, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.5 or the range between any of the above values; more preferably 1:(4 - 6):(1 - 3).

[0032] Preferably, the metal complexing agent includes sodium pyrophosphate and / or sodium ethylenediaminetetraacetate.

[0033] Preferably, the co-reducing agent includes at least one of fructose, glucose, lactose, galactose or sorbose.

[0034] Preferably, based on 100 parts by mass of the solid of the monomer, the preparation raw materials further include 0.1 - 2 parts of an electrolyte (for example, 0.1 part, 0.2 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part, 2 parts or the range between any of the above values), 0.2 - 5 parts of an emulsifier (for example, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.5 part, 2 part, 2.5 part, 3 part, 3.5 part, 4 part, 4.5 part, 5 part or the range between any of the above values) and 0.1 - 2 parts of a chain transfer agent (for example, 0.1 part, 0.2 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part, 2 part or the range between any of the above values).

[0035] In the present invention, the electrolyte includes, but is not limited to, at least one of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, and sodium tripolyphosphate; the emulsifier includes an anionic emulsifier; the anionic emulsifier includes at least one of potassium oleate, potassium disproportionated rosin, potassium stearate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, and sodium dioctylsulfonate; the chain transfer agent includes at least one of n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoacetic acid, and formic acid.

[0036] Preferably, the average particle size of the butadiene-based polymer is 80 - 320 nm, and for example, it can be 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, 220 nm, 240 nm, 260 nm, 280 nm, 300 nm, 320 nm, or the range between any of the above values.

[0037] In the present invention, the average particle size of the butadiene-based polymer can be measured by a laser nano-particle size analyzer.

[0038] In a second aspect, the present invention provides a method for preparing a butadiene-based polymer according to the first aspect, and the preparation method includes the following steps:

[0039] Mix the monomer, initiator, and solvent, and react to obtain the butadiene-based polymer.

[0040] Preferably, the mixed raw materials further include at least one of an electrolyte, an emulsifier, and a chain transfer agent.

[0041] Preferably, the solvent includes water; based on 100 parts by mass of the solid monomer, the mass of the solvent is 70 - 200 parts, and for example, it can be 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, or the range between any of the above values.

[0042] Preferably, the reaction temperature is 60 - 80 °C, and for example, it can be 60 °C, 65 °C, 70 °C, 75 °C, 80 °C, or the range between any of the above values.

[0043] Preferably, the degree of the reaction is that the monomer conversion rate ≥ 85%, and for example, it can be 85%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, or the range between any of the above values.

[0044] In the present invention, during the reaction process, samples are taken, and the monomer conversion rate is measured by the drying method until the monomer conversion rate ≥ 85%, which is the end point of the reaction.

[0045] In the present invention, the butadiene-based polymer may be a dry polymer or a butadiene-based latex; among them, by reacting to obtain a butadiene-based latex, and using conventional methods (such as coagulation) etc. on the obtained butadiene-based latex, a butadiene-based dry polymer can be obtained.

[0046] In the present invention, the butadiene-based polymer emulsion obtained by reaction can be coagulated and then used in subsequent applications; or the butadiene-based polymer emulsion obtained by reaction can be directly used in subsequent applications.

[0047] In the third aspect, the present invention provides an ABS rubber powder, and the raw materials for preparing the ABS rubber powder include the butadiene-based polymer described in the first aspect.

[0048] In the present invention, the raw materials for preparing the ABS rubber powder further include a comonomer, an initiator, an emulsifier, and a chain transfer agent; based on 100 parts by weight of the dry basis of the butadiene-based polymer, the amount of the comonomer used is 20 to 150 parts, for example, it can be 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, or the range between any of the above values; the amount of the initiator used is 0.5 to 25 parts, for example, it can be 0.5 parts, 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, or the range between any of the above values; the amount of the emulsifier used is 4.5 to 15.5 parts, for example, it can be 4.5 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, or the range between any of the above values; the amount of the chain transfer agent used is 1 to 6 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, or the range between any of the above values.

[0049] In the present invention, the comonomer includes an aromatic vinyl monomer and an alkenyl cyanide monomer; the mass percentage content of the aromatic vinyl monomer in the comonomer is 60 to 90%, for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, or the range between any of the above values.

[0050] In the present invention, for the types of comonomer, initiator, emulsifier, and chain transfer agent in the raw materials for preparing the ABS rubber powder, there are no special restrictions, and conventional auxiliaries in the art can be used, including but not limited to the initiator, emulsifier, chain transfer agent, etc. used in preparing the butadiene-based polymer.

[0051] In the present invention, the preparation method of the ABS rubber powder can be carried out by using a conventional method. Exemplarily, the preparation method includes: mixing a butadiene-based polymer with a comonomer, an initiator, an emulsifier, a chain transfer agent, and a solvent, reacting at 40-80 °C for 2-8 h to obtain an ABS graft latex; then mixing the graft latex with a coagulant and a solvent, coagulating at 70-100 °C for 1-3 h, and then coagulating at 80-110 °C for 0.5-2.5 h, washing and drying to obtain the ABS rubber powder.

[0052] In the present invention, the butadiene-based polymer is a latex with a solid content of 20-65% and an average particle size of 80-320 nm; the coagulant includes, but is not limited to, one or more of sulfuric acid, hydrochloric acid, acetic acid, calcium sulfate, magnesium sulfate, calcium carbonate, or calcium chloride; the solvent includes, but is not limited to, water.

[0053] In the present invention, based on 100 parts by mass of the ABS graft latex, the dosage of the coagulant is 5-15 parts, for example, it can be 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 15 parts, or the range between any of the above values; the mass of the solvent is 300-700 parts, for example, it can be 300 parts, 350 parts, 400 parts, 450 parts, 500 parts, 550 parts, 600 parts, 650 parts, 700 parts, or the range between any of the above values.

[0054] Fourthly, the present invention provides an ABS resin composition, and the ABS resin composition includes the ABS rubber powder described in the third aspect.

[0055] Preferably, by weight, the ABS resin composition includes 10-30 parts of ABS rubber powder (for example, it can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, or the range between any of the above values, more preferably 15-25 parts) and 70-90 parts of an aromatic vinyl-vinyl cyanide copolymer (for example, it can be 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, 84 parts, 85 parts, 86 parts, 88 parts, 90 parts, or the range between any of the above values, more preferably 75-85 parts).

[0056] Preferably, based on parts by weight, the ABS resin composition further comprises 0.5 to 5 parts of an auxiliary agent, for example, it can be 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5 parts or the range between any of the above values, and more preferably 0.5 to 2.5 parts.

[0057] In the present invention, the auxiliary agent can be selected according to actual needs, including but not limited to antioxidants, lubricants, etc.

[0058] In the present invention, the antioxidant includes but not limited to at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 445, antioxidant 1098.

[0059] In the present invention, the lubricant includes but not limited to at least one of ethylene bisstearamide, erucamide, zinc stearate or silicone oil.

[0060] In the present invention, the aromatic vinyl-vinyl cyanide copolymer includes but not limited to styrene-acrylonitrile copolymer.

[0061] Preferably, the oxidation induction time of the ABS resin composition is ≥20 min, more preferably the oxidation induction time is ≥30 min, and particularly preferably the oxidation induction time is ≥40 min.

[0062] Preferably, when treated at 100 °C for 24 h, the change value of the yellowness index of the ABS resin composition is ≤4.5, more preferably the change value of the yellowness index is ≤3.5, and particularly preferably the change value of the yellowness index is ≤1.5.

[0063] The numerical ranges described in the present invention not only include the above-listed point values, but also include any point values between the above numerical ranges not listed. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0064] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0065] For the butadiene-based polymer provided by the present invention, a specific composition of initiator is selected, and at the same time, by controlling the content of 1,2-butadiene structural units in the molecular structure of the butadiene-based polymer within a specific range, the stereoregularity of the butadiene-based polymer can be adjusted, reducing degradation, branching and crosslinking, etc. of the butadiene-based polymer during subsequent application processes, improving the heat resistance and weather resistance of the butadiene-based polymer, so that the oxidation induction time of the ABS resin material including the butadiene-based polymer is long, and the color value change before and after heat treatment is small. Detailed embodiments

[0066] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0067] The materials used in the present invention can all be obtained by purchasing commercially or prepared by conventional methods; unless otherwise specified, the materials used in the present invention are as follows.

[0068] Monomers: Butadiene was purchased from Guangdong Kete Gas Co., Ltd.; Styrene was purchased from InnoChem; Acrylonitrile was purchased from InnoChem.

[0069] Initiator system: Potassium persulfate, from Shanghai Reagent; Ammonium persulfate, from Shanghai Reagent; Cumene hydroperoxide, from InnoChem; 2,2'-Azobis(2-methylpropionitrile), from InnoChem; Ferrous sulfate, from Shanghai Reagent; Sodium ethylenediaminetetraacetate (EDTA), from Shanghai Reagent; Fructose, from Macklin.

[0070] Emulsifiers: Potassium disproportionated rosin, from InnoChem; Potassium oleate, from Aladdin; Potassium stearate, from Macklin.

[0071] Chain transfer agent: Potassium carbonate.

[0072] In the present invention, the test method for the contents of 1,2-butadiene structural unit, trans-1,4-butadiene structural unit and cis-1,4-butadiene structural unit in the butadiene-based polymer refers to the industry standard: SH / T 1727-2017, "Determination of Microstructure of Butadiene Rubber - Infrared Spectroscopy Method"; specifically as follows:

[0073] Dissolve the butadiene-based polymer in ethanol / toluene (ETA) solvent (volume ratio 1:1) for 2 - 3 h. Take the dissolved rubber solution to coat a film and test the infrared. If gel appears during the dissolution process, it needs to be filtered off. Take 3 - 4 drops of the rubber solution to coat a film on a KBr salt plate, and test after the solvent volatilizes. Test in the range of 2400 cm -1 ~600 cm -1 The specific calculation formula is as follows:

[0074] (1) Relative absorbance

[0075]

[0076] where A 728 represents the absorbance of the cis-1,4-butadiene structural unit at 728 cm -1 , A 965 represents the absorbance of the trans-1,4-butadiene structural unit at 965 cm -1 , and A 909 represents the absorbance of the cis-1,2-butadiene structural unit at 909 cm -1 .

[0077] (2) Microstructure content (g / L)

[0078] C cis = 1.7896 × A 728 % - 0.0253 × A 965 % - 0.0085 × A 909 %

[0079] C trans = 0.3971 × A 965 % - 0.0502 × A 728 % - 0.0142 × A 909 %

[0080] C vinyl = 0.2954 × A 909 % - 0.0075 × A 728 % - 0.0065 × A 965 %

[0081] Among them, C cis represents the mass content (g / L) of the cis-1,4-butadiene structural unit, C trans represents the mass content (g / L) of the trans-1,4-butadiene structural unit, C vinyl represents the mass content (g / L) of the 1,2-butadiene structural unit.

[0082] (3) Relative microstructure content

[0083]

[0084] Among them, C cis % represents the mass percentage of the cis-1,4-butadiene structural unit, C trans % represents the mass percentage of the trans-1,4-butadiene structural unit, C vinyl % represents the mass percentage of the 1,2-butadiene structural unit.

[0085] In the present invention, a laser nano-particle size analyzer is used to directly measure the average particle size of the butadiene-based polymer emulsion obtained by reaction.

[0086] Examples 1 to 19, Comparative Examples 1 to 5

[0087] Examples 1 to 19 and Comparative Examples 1 to 5 respectively provide a butadiene-based polymer, and the butadiene-based polymer exists in the form of an emulsion; by weight, the preparation raw materials of the butadiene-based polymer, the theoretical mass percentage content (V 理 ) of the 1,2-butadiene structural unit, the actual mass percentage content (V 实) The actual mass percentage content of the trans-1,4-butadiene structural unit (Trans-1,4), the actual mass percentage content of the cis-1,4-butadiene structural unit (Cis-1,4), and the average particle size are shown in Tables 1 to 4; among them, " / " indicates that there is no such component in the formulation; it should be noted that in Tables 1 to 4, "I 2 or I 2 ′" means that when the initiator is selected from redox initiators, it is I 2 ′, and when the initiator is not a redox initiator, it is an oil-soluble initiator and / or a water-soluble initiator, which is I 2 .

[0088] The preparation method of the butadiene-based polymer includes: according to the formulation amount, adding monomers, initiators, electrolytes, emulsifiers, chain transfer agents, and deionized water to a reactor, mixing evenly, heating to 68 °C, starting the polymerization reaction. During the reaction process, samples are taken. When the monomer conversion rate is tested to be 90% by the drying method, the reaction reaches the end point, and the reaction is stopped to obtain a butadiene-based polymer with a solid content of 30-65%.

[0089] Table 1

[0090]

[0091]

[0092] Table 2

[0093]

[0094] Table 3

[0095]

[0096]

[0097] Table 4

[0098]

[0099]

[0100] Application Example 1

[0101] This application example provides an ABS rubber powder, and the preparation method of the ABS rubber powder includes:

[0102] (1) Add the butadiene-based polymer emulsion into a reaction kettle. Then, based on 100 parts of the dry basis of the butadiene-based polymer emulsion, add 0.015 part of ferric sulfate and 3 parts of sodium formaldehyde sulfoxylate, and stir evenly. Heat the reaction kettle to 67 °C, and add 2.51 parts of cumene hydroperoxide, 75 parts of styrene, 25 parts of acrylonitrile, 1.5 parts of tert-dodecyl mercaptan, 5 parts of sodium dodecyl sulfonate, and 175 parts of deionized water. Continuously dropwise add for 2 h, and continue to react for 5 h after heating is completed to obtain an ABS graft latex.

[0103] (2) Mix 100 parts of the ABS graft latex obtained in step (1) with 500 parts of deionized water and 10 parts of magnesium sulfate. Start stirring and heat to 85 °C, stir for 2 h, then raise the temperature to 95 °C, continue to stir for 1.5 h, and then wash the above suspension with deionized water for multiple times, and then perform drying. After constant weight, the ABS rubber powder is obtained.

[0104] Among them, the butadiene-based polymer emulsions in step (1) are respectively provided in Examples 1 to 19 and Comparative Examples 1 to 5, and the obtained ABS rubber powders are numbered ABS1 to ABS19 and ABSd1 to ABSd5 respectively.

[0105] Application Example 2-1 to Application Example 2-19

[0106] Provide an ABS resin composition. Based on solid weight parts, the ABS resin composition includes 20 parts of ABS rubber powder, 78 parts of aromatic vinyl-vinyl cyanide copolymer (AS resin, grade: KFA-130H), 1 part of antioxidant (antioxidant 1010 and antioxidant 168 with a mass ratio of 1:1), and 1 part of lubricant (ethylene bisstearamide); the ABS rubber powders are respectively ABS1 to ABS19.

[0107] Application Example 2-20

[0108] This application example provides an ABS resin composition. Based on solid weight parts, the ABS resin composition includes 28 parts of ABS rubber powder, 70 parts of aromatic vinyl-vinyl cyanide copolymer (AS resin, grade: KFA-130H), 1 part of antioxidant (antioxidant 1010 and antioxidant 168 with a mass ratio of 1:1), and 1 part of lubricant (ethylene bisstearamide); the ABS rubber powder is ABS1.

[0109] Comparative Application Example 2-1 to Comparative Application Example 2-5

[0110] Provided is an ABS resin composition. In parts by solid weight, the ABS resin composition comprises 20 parts of ABS rubber powder, 78 parts of an aromatic vinyl-vinyl cyanide copolymer (AS resin, grade: KFA-130H), 1 part of an antioxidant (antioxidant 1010 and antioxidant 168 with a mass ratio of 1:1), and 1 part of a lubricant (ethylene bisstearamide); the ABS rubber powder is respectively ABSd1 to ABSd5.

[0111] Performance test

[0112] (1) Heat resistance: According to ASTM D1925-70(1988)e1, the change value (ΔYI) of the yellowness index of the ABS composition before and after being placed in an oven at 100 °C for 24 h was tested.

[0113] (2) Oxidation induction time: According to GB / T 19466.6-2009, "Plastics - Differential scanning calorimetry (DSC) - Part 6: Determination of oxidation induction time (isothermal OIT) and oxidation induction temperature (dynamic OIT)".

[0114] The specific test results of the ABS resin compositions provided in Application Examples 2-1 to 2-20 and Comparative Application Examples 2-1 to 2-5 are shown in Table 5.

[0115] Table 5

[0116]

[0117]

[0118] As can be seen from Table 5, for the butadiene-based polymer provided by the present invention, by controlling the content of 1,2-butadiene structural units in the molecular structure of the butadiene-based polymer within a specific range, the oxidation induction time of the ABS resin composition prepared from the butadiene-based polymer is long, the oxidation induction time ≥ 20 min; the change value of the YI value before and after heat treatment is small, ΔYI ≤ 4.5; more preferably, by controlling the initiator composition and content to satisfy a specific formula with the theoretical content of 1,2-butadiene structural units, a butadiene-based polymer containing a specific content of 1,2-butadiene structural units can be obtained, and the actual content of 1,2-butadiene structural units is closer to the theoretical content. On the premise of ensuring a relatively high reaction activity of the butadiene-based polymer, it is beneficial to prepare an ABS resin material with better heat resistance and weather resistance.

[0119] It can be seen from the comparative examples that the composition of the initiator does not satisfy the formula relationship with the mass content of 1,2-butadiene structural units in the butadiene-based polymer, the content of the obtained 1,2-butadiene structural units is too high, and the heat resistance and weather resistance of the obtained ABS resin material are poor.

[0120] The specific embodiments described above further elaborate on the objective, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only for the specific embodiments of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A butadiene polymer, characterized in that: The raw materials for preparing the butadiene-based polymer include monomers and initiators; By weight, the monomers include 75 to 100 parts of butadiene, 0 to 12.5 parts of aromatic vinyl monomers, and 0 to 12.5 parts of vinyl cyanide monomers; The initiator includes a first initiator and / or a second initiator; the first initiator includes an oil-soluble initiator and a water-soluble initiator; the second initiator includes a redox initiator; In the molecular structure of the butadiene-based polymer, the mass percentage content of the 1,2-butadiene structural unit is ≤30%.

2. The butadiene polymer according to claim 1, characterized in that In the molecular structure of the butadiene-based polymer, the mass percentage content of the 1,2-butadiene structural unit is ≤20%, and more preferably the mass percentage content of the 1,2-butadiene structural unit is 5 to 15%; Preferably, the molecular structure of the butadiene-based polymer further includes a trans-1,4-butadiene structural unit and a cis-1,4-butadiene structural unit; Preferably, the mass percentage content of the trans-1,4-butadiene structural unit in the butadiene-based polymer is 30 to 60%, and more preferably the mass percentage content of the trans-1,4-butadiene structural unit is 40 to 55%; Preferably, the mass percentage content of the cis-1,4-butadiene structural unit in the butadiene-based polymer is 20 to 50%, and more preferably the mass percentage content of the cis-1,4-butadiene structural unit is 35 to 45%.

3. The butadiene polymer according to claim 1 or 2, characterized in that: Based on 100 parts of the solid mass of the monomers, the mass of the initiator is 0.01 to 8 parts, and more preferably the mass of the initiator is 0.1 to 7 parts; Preferably, the mass content of the initiator and the 1,2-butadiene structural unit in the butadiene-based polymer satisfies the following relationship: I = I1 + I2 15 ≤ V ≤ 30%; and / or, I = I2′ + I3 5 ≤ V < 15%; Where, I1=100×130 lg(V / 4) ; I2 = 100 × 130 ln(1.5V) ; I3 = 100 × 130 lgV ; I2′=100I2; Wherein, V is the theoretical mass content of the 1,2-butadiene structural unit in the butadiene-based polymer; I is the total mass of the initiator; I1 is the mass of the water-soluble initiator; I2 is the mass of the oil-soluble initiator; I3 is the mass of the reducing agent in the redox initiator.

4. The butadiene polymer according to any one of claims 1 to 3, characterized in that The oil-soluble initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, benzoyl peroxide, or di(2-ethylhexyl) peroxydicarbonate; Preferably, the water-soluble initiator includes at least one of potassium persulfate, ammonium persulfate, hydrogen peroxide, sodium persulfate, azobisisobutylamidine hydrochloride, azobisisobutimidazoline hydrochloride, azodicyanovaleric acid, or azodiisopropylimidazoline; Preferably, the oxidizing agent in the redox initiator includes at least one of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyric acid dimethyl ester, cumene hydroperoxide, benzoyl peroxide, or di(2-ethylhexyl) peroxydicarbonate; Preferably, the reducing agent in the redox initiator includes at least one of ferrous sulfate, ferric chloride, sodium formaldehyde sulfoxylate, sodium metabisulfite, or tetraethyl pentanediamine; Preferably, when the initiator is selected from redox initiators, the raw materials for preparation further include a metal complexing agent and a co-reducing agent; Preferably, the mass ratio of the reducing agent, the metal complexing agent and the auxiliary reducing agent is 1:(3-7):(0.5-3.5); Preferably, the metal complexing agent comprises tetrasodium pyrophosphate and / or sodium ethylenediaminetetraacetate; Preferably, the co-reducing agent includes at least one of fructose, glucose, lactose, galactose or sorbitol.

5. The butadiene polymer according to any one of claims 1 to 4, characterized in that Based on 100 parts of the solid mass of the monomer, the preparation raw material further comprises 0.1 to 2 parts of electrolyte, 0.2 to 5 parts of emulsifier and 0.1 to 2 parts of chain transfer agent; Preferably, the average particle size of the butadiene-based polymer is 80 to 320 nm.

6. A method for preparing a butadiene-based polymer according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: The monomer, initiator and solvent are mixed and reacted to obtain the butadiene polymer.

7. The preparation method according to claim 6, characterized in that: The mixed raw materials also include at least one of an electrolyte, an emulsifier and a chain transfer agent; Preferably, the solvent includes water; based on 100 parts of the solid mass of the monomer, the mass of the solvent is 70 to 200 parts; Preferably, the reaction temperature is 60-80°C; Preferably, the degree of the reaction is to react until the monomer conversion rate is ≥ 85%.

8. An ABS rubber powder, characterized in that: The raw materials for preparing the ABS rubber powder include the butadiene polymer described in any one of claims 1 to 5.

9. An ABS resin composition, characterized in that: The ABS resin composition comprises the ABS rubber powder according to claim 8.

10. The ABS resin composition according to claim 9, characterized in that: The oxidation induction time of the ABS resin composition is ≥20 min; Preferably, after being treated at 100° C. for 24 hours, the yellowness index change value of the ABS resin composition is ≤4.5.

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