阅读说明：本技术 一种abs接枝胶乳的制备方法及制备的abs树脂 (Preparation method of ABS (acrylonitrile-butadiene-styrene) grafted latex and prepared ABS resin ) 是由 赵以兵 韩强 孙一峰 黎源 于 2021-01-18 设计创作，主要内容包括：本发明公开了一种ABS接枝胶乳的制备方法,包括制备聚丁二烯胶乳,然后由聚丁二烯胶乳制备具有交联亲水层的聚丁二烯胶乳,最后将具有交联亲水层的聚丁二烯胶乳与苯乙烯、丙烯腈接枝聚合制得ABS接枝胶乳。以本发明所述ABS接枝胶乳制备得到的ABS树脂具有高抗冲击性能,抗冲击性能可高达370J/m以上。(The invention discloses a preparation method of ABS graft latex, which comprises the steps of preparing polybutadiene latex, preparing polybutadiene latex with a cross-linked hydrophilic layer from the polybutadiene latex, and finally carrying out graft polymerization on the polybutadiene latex with the cross-linked hydrophilic layer, styrene and acrylonitrile to obtain the ABS graft latex. The ABS resin prepared by the ABS graft latex has high impact resistance which can reach more than 370J/m.)

1. The preparation method of the ABS graft latex is characterized by comprising the following steps:

1) preparation of the polybutadiene latex: adding butadiene, an emulsifier, an electrolyte, a chain transfer agent, an initiator and water into a reaction kettle, uniformly stirring, heating the reaction kettle to a temperature of preferably 55-85 ℃ for polymerization, adding a hydrophilic monomer into the reaction kettle for continuous reaction when the butadiene conversion rate is 60-80%, cooling the reaction kettle to a temperature of preferably 35-65 ℃ when the butadiene conversion rate is 92-98%, adding zinc oxide into the reaction kettle, uniformly stirring, and preferably preserving heat for 0.2-2 hours after heat preservation to obtain polybutadiene latex;

2) preparation of a polybutadiene latex with a crosslinked hydrophilic layer: adding the polybutadiene latex, the weak hydrophilic monomer, the crosslinking monomer, the emulsifier, the reducing aid, the reducing agent, the complexing agent, the initiator and water into a reaction kettle, uniformly stirring, heating the reaction kettle to preferably 40-70 ℃ for reaction, and obtaining the polybutadiene latex with the crosslinking hydrophilic layer when the residual quantity of the weak hydrophilic monomer is less than or equal to 200 ppm;

3) preparation of ABS graft latex: adding the polybutadiene latex with the crosslinking hydrophilic layer, styrene, acrylonitrile, an optional emulsifier, a chain transfer agent, a reducing agent, an initiator and water into a reaction kettle, uniformly stirring, heating the reaction kettle to preferably 70-90 ℃ to perform polymerization reaction, and obtaining the ABS grafted latex when the acrylonitrile content is less than or equal to 2000 ppm.

2. The preparation method according to claim 1, wherein the amount of each component in step 1) is: 90-100 parts of butadiene, 1-8 parts of emulsifier, 0.1-3 parts of electrolyte, 0.1-3 parts of chain transfer agent, 0.1-1 part of initiator, 90-140 parts of water, 1-10 parts of hydrophilic monomer and 0.1-5 parts of zinc oxide by weight.

3. The method according to claim 1 or 2, wherein the components in step 2) are used in the following amounts: 50-90 parts of polybutadiene latex, 5-20 parts of weak hydrophilic monomer, 1-5 parts of crosslinking monomer, 1-5 parts of emulsifier, 0.001-0.010 part of auxiliary reducing agent, 0.1-1.0 part of reducing agent, 0.01-0.1 part of complexing agent, 0.1-1.0 part of initiator and 100-150 parts of water in parts by weight.

4. The method according to any one of claims 1 to 3, wherein the components in step 3) are used in the following amounts: 100-120 parts of polybutadiene latex with a crosslinking hydrophilic layer, 25-35 parts of styrene, 5-15 parts of acrylonitrile, 0-5 parts of emulsifier, 0.1-3 parts of chain transfer agent, 0.1-1 part of reducing agent, 0.1-1.0 part of initiator and 140-160 parts of water in parts by weight.

5. The method according to any one of claims 1 to 4, wherein the hydrophilic monomer in step 1) is one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and preferably acrylic acid.

6. The method according to any one of claims 1 to 5, wherein the electrolyte in step 1) is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium tripolyphosphate, preferably potassium carbonate; and/or the chain transfer agent in the steps 1) and 3) is one or two of n-dodecyl mercaptan and tert-dodecyl mercaptan, and the tert-dodecyl mercaptan is preferred.

7. The method according to any one of claims 1 to 6, wherein the weakly hydrophilic monomer in step 2) has a solubility in 100 parts by weight of water at 20 ℃ of 1.5 to 7.5 parts by weight, and is preferably one or more of ethyl acrylate, methyl methacrylate, acrylonitrile, methyl acrylate, and vinyl acetate.

8. The production method according to any one of claims 1 to 7, characterized in that the crosslinking monomer in step 2) is one or both of allyl methacrylate and diallyl maleate, preferably allyl methacrylate; and/or the presence of a gas in the gas,

the complexing agent is one or more of aminocarboxylate and phosphate, preferably one or more of trisodium nitrilotriacetate, disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate, sodium pyrophosphate and sodium hexametaphosphate, and more preferably sodium pyrophosphate; and/or the presence of a gas in the gas,

the auxiliary reducing agent is one or more of ferrous sulfate, ferrous chloride and sodium bisulfite, preferably ferrous sulfate; and/or the presence of a gas in the gas,

the reducing agent in the steps 2) and 3) is one or more of sodium hydrosulfite, sodium formaldehyde sulfoxylate, isoascorbic acid, glucose and lactose, and glucose is preferred.

9. The method according to any one of claims 1 to 8, wherein the emulsifier in steps 1) to 3) is an anionic emulsifier, preferably one or more of sodium dodecyl sulfate, potassium oleate, potassium disproportionate abietate, sodium dodecyl benzene sulfonate and sodium dioctyl sulfosuccinate; and/or the initiator is selected from one or more of inorganic peroxides and organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide and cumene hydroperoxide.

10. An ABS resin prepared from the ABS graft latex of any one of claims 1 to 9.

Technical Field

The invention belongs to the field of macromolecules, and particularly relates to a preparation method of ABS graft latex and prepared ABS resin.

Background

ABS resin generally refers to a terpolymer of butadiene, styrene and acrylonitrile. The ABS resin has the characteristics of good chemical resistance, good impact resistance, easy processing and forming and the like, so that the ABS resin can be widely applied to various fields such as household appliances, automobiles and the like. At present, ABS resin in the industry is mostly prepared by adopting an emulsion grafting-SAN blending method. The method comprises three parts of preparation of dispersed phase ABS rubber powder, preparation of continuous phase SAN resin and mixing, extruding and granulating of the dispersed phase ABS rubber powder and the continuous phase SAN resin. The preparation process comprises the following steps: the ABS rubber powder is prepared by firstly carrying out emulsion polymerization on butadiene monomer to obtain polybutadiene latex, then grafting a copolymer of styrene and acrylonitrile on the polybutadiene latex to obtain ABS graft latex with a core-shell structure, and finally coagulating and drying the ABS graft latex to obtain the ABS rubber powder; the SAN resin is obtained by copolymerizing styrene and acrylonitrile according to a specified proportion by adopting a continuous bulk method; and (3) blending and extruding the ABS rubber powder and the SAN resin to obtain the ABS resin.

As is known from the grafting methods described above, the grafting reaction of styrene and acrylonitrile on the polybutadiene latex is a free radical-initiated copolymerization. The initiator free radical takes active hydrogen on the polybutadiene molecular chain or attacks the residual double bonds on the polybutadiene molecular chain to form polybutadiene long-chain free radical, and the free radical initiates the graft monomer (styrene and acrylonitrile) to carry out copolymerization reaction. In order to ensure that the ABS rubber powder serving as a dispersed phase has good compatibility with the SAN resin serving as a continuous phase matrix, the copolymerization ratio of styrene and acrylonitrile in the grafting process is required to be consistent with that of styrene and acrylonitrile in the SAN resin serving as the continuous phase as much as possible. However, in the grafting process, due to similar compatibility, styrene is more easily diffused into polybutadiene latex for internal grafting reaction than acrylonitrile, which can cause the content of styrene and acrylonitrile in the grafting reaction outside polybutadiene latex particles to be reduced, and because the polymerization activity of acrylonitrile monomer is lower than that of styrene, the enrichment of acrylonitrile monomer in the grafting reaction outside polybutadiene latex particles causes the copolymerization ratio of the styrene and acrylonitrile copolymer segments to deviate from the copolymerization ratio of the formula design, and the compatibility of the ABS rubber powder prepared by the ABS rubber powder and SAN resin in the blending extrusion process is reduced, so that the impact resistance of the prepared ABS resin is reduced.

In order to obtain ABS resins with high impact resistance, patent application CN109071916A discloses a process for the preparation of ABS graft copolymers. According to the method, the reactive phosphate ester emulsifier is added in the grafting process, and the ABS resin with good hue and high impact strength is obtained by utilizing the characteristic that the emulsifier can consume impurities such as metal ions in a system. However, the reactive phosphate ester emulsifier adopted by the method is expensive and is not beneficial to large-scale industrial production. Patent application CN108368210A discloses a thermoplastic resin and a method for preparing a thermoplastic resin composition. The patent is made by mixing large particles And small particle sizeThe polybutadiene latex is mixed and grafted together, and the ABS resin with high impact resistance is obtained by utilizing the characteristics of large specific surface area and easy graft reaction of the latex with small particle size. The method needs to prepare two kinds of latex with different particle diameters respectively, and has the disadvantages of complicated production process and low production efficiency.

Therefore, it is required to develop a method for preparing an ABS graft latex for preparing a high impact ABS resin, which is suitable for industrialization.

Disclosure of Invention

The invention aims to provide a preparation method of ABS graft latex, and ABS resin prepared from the ABS graft latex has high impact resistance which can reach more than 370J/m, has high production efficiency, and is suitable for industrial application.

In order to achieve the above purpose, the invention is realized by the following technical scheme:

a preparation method of ABS graft latex comprises the following steps: adding hydrophilic monomer and crosslinking with zinc oxide in the preparation process of polybutadiene latex, then cladding the obtained latex with weak hydrophilic monomer and crosslinking monomer to obtain polybutadiene latex with a crosslinking hydrophilic layer, and finally grafting styrene and acrylonitrile on the polybutadiene latex with the crosslinking hydrophilic layer to obtain the ABS grafted latex.

The ABS graft latex with a core-interlayer-shell structure can be obtained by the method of the invention:

modifying the core surface by hydrophilic crosslinking:

in the later stage of preparing polybutadiene latex by butadiene polymerization, adding hydrophilic monomer, then adding zinc oxide for crosslinking to obtain polybutadiene latex (core) with surface hydrophilic modification and zinc oxide crosslinking;

intermediate layer

Grafting and polymerizing a weak hydrophilic monomer and a crosslinking agent on the surface layer of the butadiene latex to further strengthen the hydrophilic crosslinking modification of the surface of the polybutadiene latex, so that monomers such as styrene and the like can be prevented from entering the interior of the polybutadiene latex;

normal grafting

And (3) grafting styrene and acrylonitrile on the modified polybutadiene latex to obtain the ABS grafted latex.

The added compact hydrophilic crosslinking layer can effectively prevent the graft monomer from diffusing into the polybutadiene rubber particles when the polybutadiene is grafted, so that the internal grafting is reduced, the external grafting rate is increased, and the compatibility of the polybutadiene rubber particles and the substrate SAN resin is enhanced; on the other hand, the hard monomer is grafted into the polybutadiene rubber, so that the rubber elasticity is not reduced; the ABS graft latex with good compatibility and high toughening efficiency can be obtained after the combination.

As a preferred embodiment, a method for preparing an ABS graft latex comprises the steps of:

1) preparation of the polybutadiene latex: adding butadiene, an emulsifier, an electrolyte, a chain transfer agent, an initiator and water into a reaction kettle, uniformly stirring, heating the reaction kettle to a temperature of preferably 55-85 ℃ for polymerization, adding a hydrophilic monomer into the reaction kettle for continuous reaction when the butadiene conversion rate is 60-80%, cooling the reaction kettle to a temperature of preferably 35-65 ℃ when the butadiene conversion rate is 92-98%, adding zinc oxide into the reaction kettle, uniformly stirring, and preferably preserving heat for 0.2-2 hours after heat preservation to obtain polybutadiene latex;

2) preparation of a polybutadiene latex with a crosslinked hydrophilic layer: adding the polybutadiene latex, the weak hydrophilic monomer, the crosslinking monomer, the emulsifier, the reducing aid, the reducing agent, the complexing agent, the initiator and water into a reaction kettle, uniformly stirring, heating the reaction kettle to preferably 40-70 ℃ for reaction, and obtaining the polybutadiene latex with the crosslinking hydrophilic layer when the residual quantity of the weak hydrophilic monomer is less than or equal to 200 ppm;

3) preparation of ABS graft latex: adding the polybutadiene latex with the crosslinking hydrophilic layer, styrene, acrylonitrile, an optional emulsifier, a chain transfer agent, a reducing agent, an initiator and water into a reaction kettle, uniformly stirring, heating the reaction kettle to preferably 70-90 ℃ to perform polymerization reaction, and obtaining the ABS grafted latex when the acrylonitrile content is less than or equal to 2000 ppm.

As a more preferred embodiment, a method for preparing an ABS graft latex comprises the steps of:

1) preparation of the polybutadiene latex: according to the weight portion, 90-100 portions of butadiene, 1-8 portions of emulsifier, 0.1-3 portions of electrolyte, 0.1-3 portions of chain transfer agent, 0.1-1 portion of initiator and 90-140 portions of water are put into a reaction kettle at one time, and are uniformly stirred and heated to 55-85 ℃ for polymerization reaction, when the butadiene conversion rate is 60-80%, 1-10 portions of hydrophilic monomer are added into the reaction kettle for continuous reaction, when the butadiene conversion rate is 92-98%, the reaction kettle is cooled to 35-65 ℃, then 0.1-5 portions of zinc oxide is added into the reaction kettle and is uniformly stirred, and the temperature is kept for 0.2-2 hours, thus obtaining the polybutadiene latex.

Preferably, 92-98 parts by weight of butadiene, 2-6 parts by weight of emulsifier, 0.5-2.5 parts by weight of electrolyte, 0.2-2.5 parts by weight of chain transfer agent, 0.2-0.9 part by weight of initiator and 130 parts by weight of 100-plus water are put into a reaction kettle at one time, the mixture is uniformly stirred and heated to 60-80 ℃ for polymerization reaction, 2-8 parts by weight of hydrophilic monomer is added into the reaction kettle for continuous reaction when the butadiene conversion rate is 65-75%, the reaction kettle is cooled to 40-60 ℃ when the butadiene conversion rate is 93-97%, then 0.5-4.5 parts by weight of zinc oxide is added into the reaction kettle and uniformly stirred, and the polybutadiene latex is obtained after heat preservation for 0.5-1.5 hours.

2) Preparation of a polybutadiene latex with a crosslinked hydrophilic layer: according to the weight portion, 50-90 portions (calculated by solid portion) of the polybutadiene latex, 5-20 portions of weak hydrophilic monomer, 1-5 portions of crosslinking monomer, 1-5 portions of emulsifier, 0.001-0.010 portion of auxiliary reducing agent, 0.1-1.0 portion of reducing agent, 0.01-0.1 portion of complexing agent, 0.1-1.0 portion of initiator and 100 portions of 150 portions of water are added into a reaction kettle and stirred uniformly, the reaction kettle is heated to 40-70 ℃ for reaction, and when the residual amount of the weak hydrophilic monomer is less than or equal to 200ppm, the polybutadiene latex with a crosslinking hydrophilic layer is obtained.

Preferably, 60-80 parts (by weight parts) of the polybutadiene latex, 6-18 parts of weak hydrophilic monomer, 1.5-4.5 parts of crosslinking monomer, 2-4 parts of emulsifier, 0.002-0.009 part of co-reducing agent, 0.2-0.9 part of reducing agent, 0.02-0.09 part of complexing agent, 0.2-0.9 part of initiator and 140 parts of 110-140 parts of water are added into a reaction kettle and stirred uniformly, the reaction kettle is heated to 45-65 ℃ for reaction, and the polybutadiene latex with the crosslinking hydrophilic layer is obtained when the residual quantity of the weak hydrophilic monomer is less than or equal to 180 ppm.

3) Preparation of ABS graft latex: adding 100-120 parts (by solid parts) of the polybutadiene latex with the crosslinking hydrophilic layer, 25-35 parts of styrene, 5-15 parts of acrylonitrile, 0-5 parts of emulsifier, 0.1-3 parts of chain transfer agent, 0.1-1 part of reducing agent, 0.1-1.0 part of initiator and 140-160 parts of water into a reaction kettle, uniformly stirring, heating the reaction kettle to 70-90 ℃ for polymerization reaction, and obtaining the ABS grafted latex when the content of acrylonitrile is less than or equal to 2000 ppm.

Preferably, 115 parts by weight (calculated by solid parts) of the polybutadiene latex with the crosslinking hydrophilic layer, 28-32 parts by weight of styrene, 8-12 parts by weight of acrylonitrile, 1-4 parts by weight of emulsifier, 0.2-2.5 parts by weight of chain transfer agent, 0.2-0.8 part by weight of reducing agent, 0.2-0.8 part by weight of initiator and 155 parts by weight of water are added into a reaction kettle and stirred uniformly, the reaction kettle is heated to 75-85 ℃ for polymerization reaction, and the ABS grafted latex is obtained when the acrylonitrile content is less than or equal to 1800 ppm.

In the invention, the hydrophilic monomer is one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, and acrylic acid is preferred.

In the present invention, the weakly hydrophilic monomer has a solubility in 100 parts by weight of water at 20 ℃ of 1.5 to 7.5 parts by weight, and is preferably one or more of ethyl acrylate, methyl methacrylate, acrylonitrile, methyl acrylate, and vinyl acetate.

In the present invention, the crosslinking monomer is one or two of allyl methacrylate and diallyl maleate, and allyl methacrylate is preferred.

In the invention, the emulsifier is an anionic emulsifier, preferably one or more of sodium dodecyl sulfate, potassium oleate, disproportionated potassium rosinate, sodium dodecyl benzene sulfonate and dioctyl sodium sulfosuccinate.

In the present invention, the chain transfer agent is one or two of n-dodecyl mercaptan and t-dodecyl mercaptan, and t-dodecyl mercaptan is preferred.

In the present invention, the initiator is selected from one or more of inorganic peroxides and organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide and cumene hydroperoxide.

In the invention, the electrolyte is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and sodium tripolyphosphate, and potassium carbonate is preferred.

In the invention, the complexing agent is aminocarboxylate or phosphate, preferably one or more of trisodium nitrilotriacetate, disodium ethylene diamine tetraacetic acid, tetrasodium ethylene diamine tetraacetic acid, sodium pyrophosphate and sodium hexametaphosphate, and more preferably sodium pyrophosphate.

In the invention, the auxiliary reducing agent is one or more of ferrous sulfate, ferrous chloride and sodium bisulfite, and ferrous sulfate is preferred.

In the invention, the reducing agent is one or more of sodium hydrosulfite, sodium formaldehyde sulfoxylate, isoascorbic acid, glucose and lactose, and glucose is preferred.

An ABS resin is prepared from the ABS graft latex. The preparation of ABS resins from ABS graft latices is conventional in the art. The specific operation of obtaining the ABS rubber powder from the ABS graft latex through coagulation, filtration, dehydration and drying can refer to pages 37-38 of the book "ABS resin production practice and application" written by Songzhou and the like, and the specific operation of obtaining the ABS resin through blending, extrusion and granulation of the ABS rubber powder and SAN resin can refer to pages 68-74 of the book.

The invention has the positive effects that:

the method comprises the steps of adding a hydrophilic monomer in the process of preparing polybutadiene latex, crosslinking by using zinc oxide, jacketing the obtained latex by using a weak hydrophilic monomer and a crosslinking monomer to obtain the polybutadiene latex with a crosslinking hydrophilic layer, and grafting styrene and acrylonitrile on the polybutadiene latex with the crosslinking hydrophilic layer to obtain the ABS grafted latex. When styrene and acrylonitrile are subjected to graft polymerization on polybutadiene latex with a crosslinking hydrophilic layer, the existence of the crosslinking hydrophilic layer can effectively prevent styrene from diffusing into polybutadiene latex particles, so that styrene and acrylonitrile monomers outside the polybutadiene latex particles can be copolymerized according to a copolymerization ratio designed by a formula, and the compatibility of ABS rubber powder prepared from the ABS graft latex and SAN resin in the blending and extruding process is improved. The ABS resin prepared by the ABS graft latex has high impact resistance which can reach more than 370J/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.

The raw material sources in the following examples and comparative examples of the present invention were obtained commercially, unless otherwise specified.

The following methods were used to test the butadiene conversion in the following examples and comparative examples of the present invention: taking 0.05g of sample into a 20ml headspace bottle, diluting the sample to 1.00g by using DMF, carrying out sample analysis by using a gas chromatograph, and testing to obtain the content of the residual butadiene monomer.

The method provided by the national standard GB/T20623-2006 is adopted for testing the residual quantity of the weak hydrophilic monomer or acrylonitrile in the latex in the following examples and comparative examples of the invention.

The impact resistance of the ABS resin in the following examples and comparative examples of the present invention was measured by the method provided in ASTM D256 for notched Izod impact strength of ABS resin at 23 ℃.

Example 1

Preparation of the polybutadiene latex: adding 90g of butadiene, 1g of sodium dodecyl sulfate, 0.1g of sodium tripolyphosphate, 1g of n-dodecyl mercaptan, 2g of tert-dodecyl mercaptan, 0.2g of sodium persulfate and 140g of water into a reaction kettle, uniformly stirring, heating the reaction kettle to 55 ℃ for polymerization, adding 1g of acrylic acid, 3g of methacrylic acid, 2g of maleic acid and 4g of fumaric acid into the reaction kettle when the butadiene conversion rate is 60.3%, continuously reacting, cooling the reaction kettle to 35 ℃ when the butadiene conversion rate is 94.9%, adding 5g of zinc oxide into the reaction kettle, uniformly stirring, and preserving heat for 2 hours to obtain the polybutadiene latex.

Examples 2 to 5

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

	Example 1	Example 2	Example 3	Example 4	Example 5
						Butadiene polymerization temperature (. degree. C.)	55	85	60	70	80
Butadiene (g)	90	98	92	100	95
						Sodium dodecyl sulfate (g)	1.00	1.00	1.00
Potassium oleate (g)		3.00		2.00	2.00
						Disproportionated rosin potassium salt (g)		1.00	1.00	2.00
Sodium dodecyl benzene sulfonate (g)				2.00	2.00
						Dioctyl sodium sulfosuccinate (g)		1.00		2.00
Sodium carbonate (g)		1.00	1.00	0.50
						Potassium carbonate (g)					1.00
Sodium bicarbonate (g)			2.00
						Potassium bicarbonate (g)		1.00			0.60
Sodium tripolyphosphate (g)	0.10	0.50
						Potassium persulfate (g)		0.10	0.55		0.55
Dicumyl peroxide (g)			0.10
						Sodium persulfate (g)	0.20			0.30
Hydrogen peroxide isopropylBenzene (g)				0.10
						Ammonium persulfate (g)			0.35	0.50
N-dodecyl mercaptan (g)	1.00	0.10	1.50	0.20
						Tert-dodecyl mercaptan (g)	2.00		1.00		1.40
Water (g)	140	130	90	100	120
						Butadiene conversion at hydrophilic monomer insertion (%)	60.3％	80％	75.2％	65.3％	69.8％
Acrylic acid (g)	1.00		2.00	0.50	4.00
						Methacrylic acid (g)	3.00		1.00		2.00
Itaconic acid (g)			2.00	0.50
						Maleic acid (g)	2.00		3.00
Fumaric acid (g)	4.00	1.00		1.00
						Butadiene conversion (g) upon insertion of zinc oxide	94.9％	94.1％	96.1％	97.2％	93.1％
Zinc oxide (g)	5.00	0.10	4.50	0.50	2.90
						Crosslinking temperature (. degree. C.) of zinc oxide	35	65	40	60	50
Zinc oxide crosslinking time (h)	2	0.2	1.5	0.5	1

Example 6

Preparation of a polybutadiene latex with a crosslinked hydrophilic layer: in parts by weight, 90g of the polybutadiene latex prepared in example 1 (in terms of solid), 8g of ethyl acrylate, 5g of methyl methacrylate, 5g of methyl acrylate, 1.5g of allyl methacrylate, 1g of sodium lauryl sulfate, 2g of potassium oleate, 2g of sodium dioctylsulfosuccinate, 0.001g of sodium hydrogen sulfite, 0.1g of sodium formaldehyde sulfoxylate, 0.01g of disodium ethylenediaminetetraacetate, 0.4g of dicumyl peroxide, 0.1g of potassium persulfate, 0.1g of sodium persulfate, 0.3g of ammonium persulfate and 140g of water were charged into a reaction vessel and stirred uniformly, the reaction vessel was heated to 40 ℃ to effect a reaction, and when the weakly hydrophilic monomer remaining amount was 182ppm, the reaction was stopped to obtain a polybutadiene latex having a crosslinked hydrophilic layer.

Examples 7 to 10

The differences between examples 7-10 and example 6 are shown in Table 2, and the remaining raw materials, experimental conditions and reaction steps are the same as those of example 6.

Table 2 examples 7-10 differences from example 6

Example 11

Preparation of ABS graft latex: 120g of the polybutadiene latex having a crosslinked hydrophilic layer prepared in example 6 (in terms of solid content), 25g of styrene, 15g of acrylonitrile, 0.1g of t-dodecylmercaptan, 0.1g of erythorbic acid, 0.1g of dicumyl peroxide and 155g of water were charged into a reaction vessel and stirred uniformly, and the reaction vessel was heated to 75 ℃ to conduct polymerization reaction, and when the acrylonitrile content was 1803ppm, the ABS graft latex was obtained.

Examples 12 to 15

The differences between examples 12-15 and example 11 are shown in Table 3, and the remaining raw materials, experimental conditions and reaction procedures were the same as those of example 11.

Table 3 examples 12-15 differences from example 11

Comparative example 1

1) Preparation of the polybutadiene latex:

adding 90g of butadiene, 1g of sodium dodecyl sulfate, 0.1g of sodium tripolyphosphate, 1g of n-dodecyl mercaptan, 2g of tert-dodecyl mercaptan, 0.2g of sodium persulfate and 140g of water into a reaction kettle, uniformly stirring, heating the reaction kettle to 55 ℃ for polymerization, and stopping the reaction when the conversion rate of butadiene is 95.3% to obtain the polybutadiene latex.

2) Preparation of ABS graft latex:

adding 120g of polybutadiene latex (calculated by solid parts) prepared in the step 1), 25g of styrene, 15g of acrylonitrile, 0.1g of tert-dodecyl mercaptan, 0.1g of isoascorbic acid, 0.1g of dicumyl peroxide and 155g of water into a reaction kettle, uniformly stirring, heating the reaction kettle to 75 ℃ for polymerization reaction, and obtaining the ABS graft latex when the content of acrylonitrile is 1821 ppm.

The invention prepares ABS resin from ABS graft latex according to the following method and tests the shock resistance:

1) 200g of the ABS graft latex prepared in examples 11 to 15 and comparative examples were weighed and added to a coagulation kettle, 2g of a 1.5% aqueous solution of sulfuric acid was added to the coagulation kettle, the coagulation kettle was heated to 90 ℃ and aged for 2 hours, the contents of the coagulation kettle were cooled to room temperature, filtered, dehydrated and dried to a water content of not more than 1%, and ABS rubber powder was obtained.

2) SA 30 of LG company is taken as a SAN resin continuous phase, ABS rubber powder prepared in the step 1) is taken as a disperse phase, and the ABS resin is obtained by mixing, extruding and granulating, wherein the polybutadiene rubber content in the prepared ABS resin is set to be 17 percent.

3) And (3) preparing a test sample strip from the ABS resin obtained in the step (2) on an injection molding machine at 180 ℃, and testing the notched izod impact strength of the ABS resin at 23 ℃ according to the ASTM D256 standard, wherein the specific results are shown in Table 4.

TABLE 4 mechanical Properties test

As can be seen from the results of the tests of examples 11 to 15 and the comparative example, the ABS resin obtained using the ABS graft latex prepared according to the present invention has higher impact resistance.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.