CN111675796A - Preparation method of polybutadiene rubber dispersion - Google Patents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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Abstract
The invention provides a preparation method of a polybutadiene rubber dispersion, which comprises the following steps: adding liquid polybutadiene rubber, butadiene, butyl acrylate, a weak hydrophilic monomer, an initiator and an optional solvent into a reaction kettle for polymerization; adding butyl acrylate, water-soluble monomer and initiator into the polymer system for copolymerization, then adding neutralizer and uniformly stirring; adding water for dispersion to obtain the polybutadiene rubber dispersion. The prepared ABS rubber powder is further prepared by the polybutadiene rubber dispersoid, and the impact strength of the ABS resin prepared by the ABS rubber powder is more than or equal to 400J/m.
Description
Technical Field
The invention belongs to the field of macromolecules, and particularly relates to a preparation method of a polybutadiene rubber dispersoid and an ABS resin prepared by taking a product prepared by the method as a raw material.
Background
The ABS resin is obtained by ternary polymerization of butadiene, styrene and acrylonitrile, and is an engineering plastic with wide application. Currently, ABS resins are prepared by both emulsion graft-bulk SAN blending and continuous bulk processes.
The emulsion grafting-bulk SAN blending method is a production process widely adopted by ABS resin at home and abroad at present. The process comprises the steps of polymerizing butadiene into polybutadiene latex by a free radical emulsion polymerization method, then carrying out graft copolymerization on styrene, acrylonitrile and the polybutadiene latex, and obtaining ABS graft powder through condensation and drying; then, blending and granulating the ABS grafted powder and SAN resin to obtain the ABS resin. In the method, the polybutadiene rubber phase is obtained by a free radical polymerization method, and the polymerization of a single double bond or the simultaneous polymerization of two double bonds of butadiene cannot be controlled during the free radical polymerization. When two double bonds of butadiene are polymerized, molecular chains of polybutadiene generated by polymerization are branched and crosslinked to form a network structure, so that the sliding among the molecular chains is hindered, the flexibility of rubber is reduced, and the impact strength of the final ABS resin is reduced.
CN102532786A discloses a method for preparing a modified ABS resin with bimodal distribution, which comprises the steps of mixing latex with large particle size and latex with super large particle size in proportion, then carrying out grafting reaction, coagulating, filtering, drying, mixing with SAN, extruding and granulating to obtain the ABS resin, wherein the impact strength of the ABS resin is about 100J/M higher than that of general-purpose ABS resin. Although the method can improve the impact strength of the ABS resin by mixing the large-particle-size latex and the extra-large-particle-size latex, the large-particle-size and extra-large-particle-size polybutadiene latexes need to be prepared respectively, and the preparation process is complex.
CN201110446719.4 discloses a styrene resin blend with particles with a three-layer structure, and preparation and application thereof, wherein an ABS resin with improved impact resistance and tensile strength is developed by synthesizing an ABS graft copolymer with a three-layer structure and then melt blending the ABS graft copolymer with a vinyl cyanide-vinyl aromatic copolymer prepared by a solution, bulk or suspension polymerization method. The method uses the traditional emulsion polymerization method to prepare the polybutadiene rubber, and does not change the molecular structure of the butadiene polymer.
Disclosure of Invention
The invention aims to provide a method for preparing a dispersion by using polybutadiene rubber prepared by an anionic polymerization method and an ABS resin prepared by using the dispersion prepared by the method. The Izod impact strength of the ABS resin prepared by the method is more than or equal to 400J/m.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a process for preparing a polybutadiene rubber dispersion, comprising the steps of:
(1) 230 parts by weight (preferably 180 parts by weight) of liquid polybutadiene rubber 170, 210 parts by weight of liquid polybutadiene rubber, 5-15 parts by weight (preferably 8-12 parts by weight) of butadiene, 5-15 parts by weight (preferably 8-12 parts by weight) of butyl acrylate, 2-10 parts by weight (preferably 4-8 parts by weight) of weakly hydrophilic monomer, 0.5-1.5 parts by weight (preferably 0.7-1.3 parts by weight) of initiator and 0-10 parts by weight (preferably 3-7 parts by weight) of optional solvent are put into a reaction kettle at one time, stirred uniformly and heated to 50-100 ℃ (preferably 60-90 ℃) for polymerization reaction;
(2) when the residual butadiene in the reaction system is less than or equal to 500ppm, adding 10-20 parts by weight (preferably 12-18 parts by weight) of butyl acrylate, 4-15 parts by weight (preferably 6-12 parts by weight) of water-soluble monomer and 0.5-1.5 parts by weight (preferably 0.7-1.3 parts by weight) of initiator for copolymerization, and when the residual butadiene in the reaction system is less than or equal to 200ppm, adding 6-10 parts by weight (preferably 7-9 parts by weight) of neutralizer and uniformly stirring;
(3) adding 300-425 parts by weight (preferably 225-330 parts by weight) of water into the product obtained in the step (2) for dispersion, thereby obtaining the polybutadiene rubber dispersion.
The solubility of the weakly hydrophilic monomer in step (1) in 100 parts by weight of water at 20 ℃ is 1.5-13.5 parts by weight, preferably 2.5-7.5 parts by weight, more preferably one or more of ethyl acrylate, vinyl acetate, methyl acrylate, acrylonitrile, and 2-hydroxypropyl methacrylate (2-HPMA).
In the step (1), 210 parts by weight of liquid polybutadiene rubber 180-one, 8-12 parts by weight of butadiene, 8-12 parts by weight of butyl acrylate, 4-8 parts by weight of weak hydrophilic monomer, 0.7-1.3 parts by weight of initiator and 3-7 parts by weight of optional solvent are put into a reaction kettle and are uniformly stirred, and the temperature is raised to 60-90 ℃ for polymerization reaction; in the step (2), 12 to 18 parts by weight of butyl acrylate, 6 to 12 parts by weight of water-soluble monomer, 0.7 to 1.3 parts by weight of initiator and 7 to 9 parts by weight of neutralizer are added; 390 parts by weight of water 312-
The liquid polybutadiene rubber is prepared by an anionic polymerization method, preferably German Langshan CB530T, CB 550T and Yingchuang
Further preferred is German Langshan CB 550T.
The temperature of the initiator in 1 hour half-life period is more than or equal to t of 60 DEG C1/2At 100 ℃ or lower, it is preferably selected from one or more of cumyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, dihexadecyl peroxydicarbonate, ditetradecyl peroxydicarbonate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, bis (3,3, 5-trimethylhexanoyl) peroxide, bis (4-methylbenzoyl) peroxide, benzoyl peroxide, dilauroyl peroxide, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, and azobisisobutyronitrile.
The boiling point of the solvent is 60-150 ℃, preferably, one or more of cyclohexane, n-hexane, n-heptane, petroleum ether, toluene and xylene.
The water-soluble monomer is one or more of itaconic acid, beta-acryloxypropionic acid, methacrylic acid and acrylic acid.
The neutralizing agent is a water-soluble amine derivative with the boiling temperature of more than or equal to 150 ℃, preferably with the boiling temperature of 150-220 ℃, and is preferably one or more of monoethanolamine, diethylenetriamine and N-ethylethanolamine.
The polybutadiene rubber dispersion of the present invention comprises: i a non-hydrophilic liquid polybutadiene rubber prepared using an anionic polymerization process; ii a high molecular chain segment polymerized by monomers containing weak hydrophilic groups, butadiene and butyl acrylate; iii a water-soluble group-containing monomer and a butyl acrylate polymerized polymer segment.
In the step 1), the liquid polybutadiene rubber is swelled by using the monomer with weak hydrophilic group, butadiene and butyl acrylate and polymerized in situ, so that the butadiene in the segment ii can be well compatible with the liquid polybutadiene rubber segment in the segment i. And in the phase inversion process of adding water for dispersion after the polymer reaction is finished, ii containing weak hydrophilic groups migrates from a miscible state with i to a water phase under the action of water, and because the ii contains a polybutadiene chain segment with good compatibility with i, the ii is closely distributed on the surface of i and cannot be separated from i. The segment iii prepared in the step 2) contains a water-soluble group, the water-soluble group extends towards the water phase under the action of water, and because the segment ii and the segment iii both contain butyl acrylate, the compatibility between the segment iii and the segment ii is better, so that the segment iii is bound by the segment ii and can not be separated from the segment ii. The segment iii is partially stretched to the water phase to form the outermost layer of the dispersion during the phase inversion process due to the strong hydrophilicity of the water-soluble groups of the segment iii, while the segment ii forms the middle layer of the segment i and the segment iii due to the acting force of the segment i and the traction force of water, and the non-hydrophilic liquid polybutadiene rubber in the segment i is positioned at the innermost layer.
The initiator used in the invention has a 1-hour half-life temperature of more than or equal to t and more than or equal to 60 DEG C1/2Not more than 100 ℃, thereby avoiding overlong reaction time at low temperature and uncontrolled reaction caused by a large amount of decomposition of the initiator due to overhigh temperature.
The water-soluble amine derivative is used as a neutralizer, the boiling temperature is more than or equal to 150 ℃, and preferably 150-220 ℃, so that the carboxyl in the water-soluble monomer extending in the water phase is fully neutralized in the reaction process, and the neutralization degree is not reduced due to quick volatilization in the reaction process.
In a second aspect, the present invention provides an ABS resin prepared using the polybutadiene rubber dispersion prepared by the method of the present invention instead of the polybutadiene latex prepared by conventional emulsion polymerization.
In the invention, the polymer powder is obtained by grafting, coagulating, filtering and drying the prepared polymer dispersoid, then the polymer powder is mechanically blended with styrene acrylonitrile copolymer (SAN resin), and the mixture is melted and granulated to obtain ABS resin, and a test sample plate is obtained by injection molding.
The invention has the beneficial effects that: the liquid polybutadiene rubber is prepared by an anionic method, and the polybutadiene rubber obtained by an anionic polymerization method different from a free radical emulsion polymerization method can selectively control the polymerization of a certain double bond in butadiene, effectively avoid the simultaneous polymerization of two double bonds of butadiene, reduce the cross-linking among molecular chains, and facilitate the slippage among the molecular chains, so that the polybutadiene rubber has higher flexibility. Compared with polybutadiene latex prepared by an emulsion method, the ABS resin prepared by the prepared dispersion has better impact strength (Izod impact strength is more than or equal to 400J/m).
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
If the source information of the raw materials in the following examples and comparative examples of the present invention is not specifically described, the raw materials used in the examples or comparative examples are commercially available;
butyl acrylate residual monomer test method: GB/T20623-.
Butadiene residual monomer test method: a sample of 0.1g was taken in a 20ml headspace bottle, diluted to 2g with DMF and analyzed by PEURBOMatrix 40 headspace sampler and Shimadzu GC 2010 gas chromatograph to determine the residual monomer content of butadiene.
Mechanical properties: universal Material testing machine (model INSTRON5567, UK), ASTM D638.
Example 1
(1) Will be provided with
170g of polybutadiene rubber, 12g of butadiene, 5g of butyl acrylate, 2g of 2-hydroxypropyl methacrylate and tert-butyl peroxyneodecanoate0.5g and 10g of cyclohexane are put into a reaction kettle at one time, stirred evenly and heated to 50 ℃ for polymerization reaction;
(2) when the residual butadiene in the step (1) is 428ppm, uniformly mixing 20g of butyl acrylate, 4g of acrylic acid and 0.5g of tert-butyl peroxyneodecanoate, and adding the mixture into a reaction kettle for polymerization; when the residual butyl acrylate in the system is 187ppm, adding 6g of ethanolamine and uniformly stirring;
(3) and (3) adding 302.5g of water into the product obtained in the step (2) for dispersing to obtain the polybutadiene rubber dispersion.
The differences between examples 2-5 and example 1 are shown in Table 1, and the remaining raw materials, experimental conditions and reaction steps are the same as those of example 1.
TABLE 1 differences between examples 2-5 and example 1
Comparative example: preparation of emulsion polybutadiene latex
The preparation method of the polybutadiene latex of this comparative example includes the following steps: 10g of potassium oleate, 1000g of butadiene, 1g of KOH, 1g of sodium persulfate and 1515g of deionized water are added into a reaction kettle, the temperature is raised to 90 ℃, polymerization reaction is carried out, and polybutadiene latex is obtained when residual butadiene is 477 ppm.
Examples of the experimentsPreparation and performance detection of ABS resin
The conventional technique in the field is to graft, coagulate, filter and dry polybutadiene latex to obtain polymer rubber powder, and then to mechanically blend and melt and granulate the polymer rubber powder and styrene acrylonitrile copolymer (SAN resin) to obtain ABS resin, and the specific operation can refer to books "ABS resin and application thereof" written in Huang Li Ben, etc.
The ABS resin was prepared from the polybutadiene rubber dispersion of the examples and the polybutadiene latex of the comparative example according to the present invention as follows: (1) 100 parts of the polybutadiene latices of examples 1 to 5 and comparative example were charged into a grafting vessel, and 0.002 part of FeSO was added thereto4Uniformly stirring, gradually heating the reaction system toGradually adding 0.15 part of cumene hydroperoxide, 11.7 parts of styrene, 4.6 parts of acrylonitrile, 0.21 part of tert-dodecyl mercaptan, 0.3 part of potassium oleate and 10 parts of deionized water at 70 ℃, continuously adding for 3 hours, and continuously reacting for 4 hours after the addition is finished to obtain the graft latex. 100 parts of the graft latex obtained above was added to a reaction vessel, heated to 95 ℃ and gradually added with 4 parts of MgSO440 parts of deionized water, keeping the temperature, uniformly stirring and reacting for 1 hour, filtering the obtained condensed emulsion by adopting a 325-mesh filter screen to obtain wet grafting powder, and drying for 4 hours at 60 ℃ and 2KPaA by adopting a vacuum drum dryer to obtain the water content<1% of graft powder. Adopting a double-screw extruder, taking Qimei PN118 as a mixed SAN phase at the temperature of 200-220 ℃, and mixing the components according to the proportion of PN 118: and (3) blending the graft powder with the blending ratio of 73/27, cooling and granulating to obtain the ABS resin.
ABS resins prepared from polybutadienes of examples 1-5 and comparative example were dried in an oven at 80 ℃ for 5 hours, respectively, and then subjected to mechanical property tests, the specific test results of which are shown in Table 2.
TABLE 2 mechanical Properties test
| Sources of polybutadiene for preparing ABS resins | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| Rubber content% | 15.3 | 15.4 | 15.8 | 15.0 | 15.1 | 19.0 |
| Impact strength J/m | 436 | 442 | 479 | 409 | 428 | 283 |
In the method, the polybutadiene rubber subjected to anionic polymerization is used as the rubber phase of the ABS resin, and the branching degree of the polybutadiene rubber molecular chain is lower than that of the polybutadiene molecular chain obtained by free radical polymerization due to different polymerization methods, so that the method is more favorable for toughening the ABS resin. As can be seen from the results of the tests of examples 1 to 5 and the comparative example, the ABS resin obtained by blending the ABS resin prepared according to the present invention with the polybutadiene latex obtained by the emulsion process in the comparative example via the graft SAN can achieve higher impact strength at a lower rubber content.
Claims (8)
1. A method for preparing a polybutadiene rubber dispersion, which is characterized by comprising the following steps:
(1) adding 230 parts by weight of liquid polybutadiene rubber 170-230, 5-15 parts by weight of butadiene, 5-15 parts by weight of butyl acrylate, 2-10 parts by weight of weak hydrophilic monomer, 0.5-1.5 parts by weight of initiator and 0-10 parts by weight of optional solvent into a reaction kettle, uniformly stirring, and heating to 50-100 ℃ for polymerization reaction;
wherein the weakly hydrophilic monomer has a solubility in 100 parts by weight of water at 20 ℃ of 1.5 to 13.5 parts by weight, preferably 2.5 to 7.5 parts by weight;
(2) when the content of the residual butadiene in the reaction system is less than or equal to 500ppm, adding 10-20 parts by weight of butyl acrylate, 4-15 parts by weight of water-soluble monomer and 0.5-1.5 parts by weight of initiator for copolymerization reaction, and when the content of the residual butyl acrylate in the system is less than or equal to 200ppm, adding 6-10 parts by weight of neutralizer and uniformly stirring;
(3) adding 300-425 parts by weight of water into the product obtained in the step (2) for dispersion to obtain the polybutadiene rubber dispersion.
2. The method for preparing polybutadiene rubber dispersion according to claim 1, wherein in step (1), liquid polybutadiene rubber 180-210 parts by weight, butadiene 8-12 parts by weight, butyl acrylate 8-12 parts by weight, weak hydrophilic monomer 4-8 parts by weight, initiator 0.7-1.3 parts by weight, and optional solvent 3-7 parts by weight are put into a reaction vessel and stirred uniformly, and the temperature is raised to 60-90 ℃ for polymerization reaction; in the step (2), 12 to 18 parts by weight of butyl acrylate, 6 to 12 parts by weight of water-soluble monomer, 0.7 to 1.3 parts by weight of initiator and 7 to 9 parts by weight of neutralizer are added; and (3) water 312-390 weight parts.
3. The method of preparing a polybutadiene rubber dispersion according to claim 1 or 2, wherein the liquid polybutadiene rubber is prepared by anionic polymerization.
4. The process for preparing a polybutadiene rubber dispersion according to any one of claims 1-3, wherein the initiator has a 1-hour half-life temperature of 60 ℃. ltoreq. t1/2At 100 ℃ or lower, preferably from the group consisting of neopentyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, dihexadecyl peroxydicarbonate, ditetradecyl peroxydicarbonate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, bis (3,3, 5-trimethylhexanoyl) peroxide, bis (4-methylbenzoyl) peroxide, benzoyl peroxide, dilauryl peroxideOne or more of lauroyl, peroxy-2-ethyl hexanoate, and azobisisobutyronitrile.
5. Process for the preparation of polybutadiene rubber dispersions according to any of claims 1-4, characterised in that the solvent has a boiling point of 60-150 ℃, preferably chosen from one or more of cyclohexane, n-hexane, n-heptane, toluene, xylene.
6. The method for preparing polybutadiene rubber dispersion according to any one of claims 1-5, wherein the water-soluble monomer is one or more of itaconic acid, β -acryloxypropionic acid, methacrylic acid, and acrylic acid.
7. Process for the preparation of polybutadiene rubber dispersions according to any of claims 1-6, characterised in that the neutralising agent is a water-soluble amine derivative with a boiling temperature of not less than 150 ℃, preferably a boiling temperature of 150 ℃ to 220 ℃.
8. An ABS resin, characterized in that, the ABS resin is prepared by using polybutadiene rubber dispersoid prepared by the method of any one of claims 1-7 as raw material.
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| CN113292771A (en) * | 2021-05-19 | 2021-08-24 | 山东高速集团有限公司创新研究院 | Rubber-plastic alloy for warm mixing and preparation method and application thereof |
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