CN110982013A

CN110982013A - Preparation method of polybutadiene latex with low gel content and prepared polybutadiene latex

Info

Publication number: CN110982013A
Application number: CN201911304316.9A
Authority: CN
Inventors: 张琴花; 韩强; 刘斌; 麻宁; 赵以兵; 刘波; 孙一峰
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2019-12-17
Filing date: 2019-12-17
Publication date: 2020-04-10
Anticipated expiration: 2039-12-17
Also published as: CN110982013B

Abstract

The invention provides a preparation method of polybutadiene latex with low gel content and the polybutadiene latex prepared by the same. The method comprises the following steps: respectively adding 1-5 parts by weight of emulsifier, 100 parts by weight of butadiene, 0.1-1 part by weight of neutralizer, 0.1-0.5 part by weight of initiator and 100-150 parts by weight of water into a reaction vessel, and heating to 60-90 ℃ for polymerization reaction; and when the butadiene conversion rate is more than or equal to 20% and less than or equal to 70%, adding allyl polyether for copolymerization reaction, and obtaining polybutadiene latex when the butadiene conversion rate is more than or equal to 90%. According to the invention, the allyl polyether monomer containing n EO chain segments and m PO chain segments is added to be copolymerized with butadiene when the conversion rate of the butadiene is 20-70%, so that the prepared polybutadiene latex has lower gel content, and the impact resistance of the ABS resin can be effectively improved.

Description

Preparation method of polybutadiene latex with low gel content and prepared polybutadiene latex

Technical Field

The invention belongs to the field of polymers, and particularly relates to a preparation method of polybutadiene latex with low gel content and the polybutadiene latex prepared by the same.

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 two methods, namely a continuous bulk method and an emulsion graft-bulk SAN blending method. The emulsion grafting-bulk SAN blending method is the mainstream method for ABS production due to the advantages of advanced technology, wide product range, good performance, small pollution and the like. In the ABS resin prepared by the emulsion grafting-bulk SAN blending method, rubber-phase polybutadiene is prepared by an emulsion polymerization mode. Factors influencing the impact strength of the ABS resin include rubber phase content, grafting rate, gel content and the like in the ABS resin; the gel is formed by cross-linking butadiene double bonds on a polybutadiene molecular chain in the emulsion polymerization process, the higher the cross-linking degree of the polybutadiene molecular chain is, the higher the gel content is, and the lower the elasticity of the rubber phase is, so that the reduction of the gel content of the polybutadiene rubber phase is beneficial to improving the elasticity of the butadiene rubber phase.

At present, the gel content of the butadiene polymer latex can be adjusted in a known manner by controlling the reaction conditions (for example: high reaction temperature and/or polymerization directly to high conversion and addition of substances acting as crosslinking to achieve high gel content, or low reaction temperature and/or stopping of the polymerization before strong crosslinking occurs and addition of molecular weight regulators (e.g.n-dodecyl mercaptan or tert-dodecyl mercaptan, etc.) to achieve low gel content). Wherein the low gel content is achieved by lowering the temperature, resulting in an increased reaction time due to a longer half-life of the initiator and a poorer polymerization activity of butadiene; by stopping the polymerization reaction in this way before strong crosslinking occurs, the butadiene conversion is reduced. At present, the method for treating the residual butadiene in the reaction kettle is to carry out flame burning treatment or purification and recycling, and either way can cause waste of resources and energy. The gel content is reduced by adding molecular weight regulator, which reduces the molecular weight of polybutadiene and further reduces ABS performance.

The prior art has made some attempts to prepare rubbers having a low gel content. Such as: patent document CN1784428A discloses: a rubber latex for use as an impact modifier having a high gel content core and a low gel content shell; high gel content cores are achieved by using graft cross-linking agents or high conversion or increasing the polymerization temperature; low gel content shells are achieved by using molecular weight regulators or low conversion or reduced temperature. The method has complex process and the latex prepared by the method has nonuniform inside and outside. Patent document CN102282184A discloses: a low gel content and low or no crosslinking emulsified rubber which achieves the low gel content characteristic of polymers by including an effective amount of a substituted phenol in the redox initiation system to the polymerization medium, but the process is limited to redox initiation systems. Patent document CN1182747A discloses: a vanadium-containing initiator system comprising one or more aromatic or heteroaromatic polycyclic hydrocarbons and an aged organic solution of vanadium tetrachloride, with the aid of which polyisoolefins having the most suitable low gel content and sufficiently high molecular weights can be prepared at relatively high temperatures. However, this initiation system cannot be used in aqueous emulsion polymerization.

Disclosure of Invention

The invention aims to provide a preparation method of polybutadiene latex with low gel content, which increases the distance between polybutadiene molecular chains by a method of adding allyl polyether for copolymerization before strong crosslinking occurs in the polymerization process of the polybutadiene latex, thereby reducing the crosslinking reaction between the polybutadiene molecular chains; further provided is a polybutadiene latex prepared by the above method, wherein the gel content is 10% -70%.

The invention is realized by the following technical scheme:

in a first aspect, the present invention provides a process for the preparation of a low gel content polybutadiene latex, comprising the steps of: respectively adding 1-5 parts by weight of emulsifier, 100 parts by weight of butadiene, 0.1-1 part by weight of neutralizer, 0.1-0.5 part by weight of initiator and 100-150 parts by weight of water into a reaction vessel, and heating to 60-90 ℃, preferably 65-85 ℃ for polymerization reaction; and when the butadiene conversion rate is more than or equal to 20% and less than or equal to 70%, adding allyl polyether for copolymerization reaction, and obtaining polybutadiene latex when the butadiene conversion rate is more than or equal to 90%.

And when the butadiene conversion rate is less than 20%, allyl polyether is added, so that the allyl polyether reacts in the latex particles too early, the allyl polyether is easily embedded, the polybutadiene chain segments on the surface layer of the polybutadiene latex and the allyl polyether copolymerization chain segments between the polybutadiene chain segments are fewer, and effective steric hindrance cannot be formed when strong crosslinking occurs in the later reaction stage. At butadiene conversion of 70% or more, partial crosslinking of the polybutadiene block occurs, and at this time, addition of allyl polyether prevents effective penetration of copolymerization into the inside of the polybutadiene latex formed, and thus prevents crosslinking of the polybutadiene block formed. Therefore, when butadiene is copolymerized with allyl polyether at a conversion of 20% to 70% in a specific range, crosslinking between polybutadiene segments can be effectively reduced, thereby reducing the gel content of the butadiene latex.

Preferably, in the method for preparing the polybutadiene latex with low gel content, the allyl polyether is added in an amount of 1-5 parts by weight.

When an excess of allyl polyether is added, this results in a reduced proportion of polybutadiene segments in the formulation, which affects the elasticity of the polybutadiene rubber phase. When the added allyl polyether is insufficient, the copolymerized allyl polyether among polybutadiene chain segments is reduced, and the steric effect is reduced, so that the crosslinking reaction among the polybutadiene chain segments cannot be effectively reduced. Therefore, it is necessary to add 1 to 5 parts by weight of allyl polyether in a specific range for copolymerization.

Preferably, the process for the preparation of the polybutadiene latex with low gel content according to the inventionIn the method, the allyl polyether contains n EO chain segments and m PO chain segments, and the structural formula is as follows: CH (CH)₂＝CHCH₂O(CH₂CH₂CH₂O)_m(CH₂CH₂O) n H, wherein n is an integer from 3 to 6, m is an integer from 6 to 18, 2 is not more than m: n is less than or equal to 6.

Adding an allyl polyether monomer containing n EO chain segments and m PO chain segments to copolymerize with butadiene, wherein n is selected from an integer of 3-6, and m is selected from an integer of 6-18, and the allyl polyether is easy to diffuse into emulsion particles in the copolymerization process due to small molecular weight; m is not less than 2: the proportion of n is less than or equal to 6, so that the PO chain segment content in the allyl polyether is higher, and the allyl polyether has stronger hydrophobicity and is easy to be compatible with the hydrophobic polybutadiene chain segment; meanwhile, EO chain segments contained in allyl polyether molecules enable the allyl polyether molecules to adsorb a certain amount of water molecules, so that the volume of the allyl chain segments in latex particles is increased, the steric effect between polybutadiene chain segments is increased, the distance between polybutadiene molecular chains is increased, and reaction sites for forming polybutadiene gel are reduced.

Preferably, in the above-mentioned method for producing a polybutadiene latex with a low gel content, the emulsifier is at least one selected from the group consisting of potassium oleate, sodium lauryl sulfate and potassium disproportionate abietate.

Preferably, in the above-mentioned method for preparing a polybutadiene latex with a low gel content, the neutralizer is at least one selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide, preferably selected from potassium carbonate and/or potassium hydroxide.

Preferably, in the method for preparing the low gel content polybutadiene latex of the present invention, the initiator is a peroxide initiator, preferably at least one of potassium persulfate, sodium persulfate and ammonium persulfate.

Preferably, in the method for preparing the polybutadiene latex with low gel content, the method for preparing the allyl polyether comprises the following steps: adding 58 parts by weight of allyl alcohol into a reaction vessel, heating to 100 ℃ and 130 ℃, adding 58m parts by weight of propylene oxide, 44n parts by weight of ethylene oxide and KOH under stirring for polymerization, wherein the addition amount of KOH is 0.3-1% based on 100% of the total weight of the allyl alcohol, the propylene oxide and the ethylene oxide;

when the conversion rate of the propylene oxide is more than or equal to 99 percent, adding phosphoric acid with the same molar quantity as KOH, uniformly stirring, and removing water generated by the reaction to obtain the allyl polyether monomer.

In a second aspect, the present invention also provides a polybutadiene latex obtained by the above-mentioned preparation method.

Preferably, in the polybutadiene latex of the present invention, the gel content of the polybutadiene latex is 10% to 70%, preferably 15% to 67%.

In a third aspect, the invention also provides an ABS resin prepared from the polybutadiene latex prepared by the preparation method.

The preparation method comprises the steps of agglomerating polybutadiene latex, grafting, agglomerating, filtering and drying to obtain polymer rubber powder, then mechanically blending the polymer rubber powder with styrene-acrylonitrile copolymer (SAN resin), performing melt granulation to obtain ABS resin, and performing injection molding to obtain a test sample plate.

The technical scheme provided by the invention has the following beneficial effects:

the gel content increases with increasing butadiene conversion in the preparation of polybutadiene latex by the emulsion process. Polybutadiene gel is formed by the fact that double bonds remaining in the polymer backbone after butadiene polymerization are opened under heating conditions or under the attack of an initiator or other free radicals, and are polymerized with double bonds in adjacent polybutadiene molecular chains. The polybutadiene gel has a network structure, so that the slippage degree between polymer molecular chains is reduced, and the deformation capability of the latex particles is weakened when the latex particles are stressed. According to the invention, when the butadiene conversion rate is 20-70%, an allyl polyether monomer containing n EO chain segments and m PO chain segments is added to be copolymerized with butadiene (wherein n is selected from an integer of 3-6, m is selected from an integer of 6-18, m is more than or equal to 2, and n is less than or equal to 6), so that the distance between polybutadiene molecular chains is increased, and the crosslinking reaction sites for forming polybutadiene gel are reducedThus allowing a low gel content of the polybutadiene latex (10% to 70%, preferably 15% to 67%). In the prior art, when the content of polybutadiene latex in the ABS resin is 15%, the notch impact strength is about 20kJ/m²The ABS resin prepared from the polybutadiene latex with the gel content of 10-70 percent is obtained under the same condition, and the notch impact strength of the ABS resin is more than or equal to 24kJ/m²Therefore, the impact resistance of the ABS resin is effectively improved.

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.

Styrene acrylonitrile copolymer (SAN resin): SAN-327, available from Daqing petrochemical division, oil and gas, Inc., China.

The conversion rate of the propylene oxide and the butadiene is obtained by detecting the residual amount of corresponding raw material monomers through GC-MS and then calculating.

Because ethylene oxide reacts more readily than propylene oxide, what remains is often propylene oxide. When the propylene oxide conversion is greater than or equal to 99%, it is considered that ethylene oxide and propylene oxide have completely reacted to form the allyl polyether monomer, and therefore the PO/EO segment ratio in the allyl polyether monomer of the present invention is the molar ratio m: n of the raw materials of propylene oxide and ethylene oxide.

Example 1Preparation of allyl polyether monomer

The preparation of allyl polyether monomer of this example includes the following steps: 58g of allyl alcohol was charged into a reaction vessel, the temperature was raised to 100 ℃ and 348g of propylene oxide, 132g of ethylene oxide and 1.61g of KOH were added with stirring to conduct polymerization. Adding phosphoric acid with the same molar weight as KOH when the conversion rate of the propylene oxide is 99.1 percent, uniformly stirring, removing generated water under the conditions of 110 ℃ and 5Kpa, and obtaining the allyl polyether monomer when the water content in the reaction product is 0.04 percent.

Examples 2 to 5Preparation of allyl polyether monomer

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
						Reaction temperature/. degree.C	100	110	120	120	130
Allyl alcohol (g)	58	58	58	58	58
						Propylene oxide (g)	348	1044	522	1044	696
Ethylene oxide (g)	132	132	176	264	132
						KOH(g)	1.61	8.64	7.56	12.29	4.43
Phosphoric acid (g)	2.82	15.12	13.23	21.51	7.75

Example 6Preparation of butadiene latex

The preparation of the butadiene latex of this example included the following steps: 10g of potassium oleate, 1000g of butadiene, 1g of KOH, 1g of sodium persulfate and 1400g of deionized water are added into a reaction kettle, the temperature is raised to 80 ℃ for polymerization, 10g of allyl polyether prepared in example 1 is added for polymerization when the butadiene conversion rate is 20%, and polybutadiene latex is obtained when the butadiene conversion rate is 91%.

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 differences between examples 7-10 and example 6

Comparative example 1

Comparative example 1 was compared to example 1, except that no allyl polyether was added.

The preparation method of the polybutadiene latex of this comparative example includes the following steps: adding 10g of potassium oleate, 1000g of butadiene, 1g of KOH, 1g of sodium persulfate and 1400g of deionized water into a reaction kettle, heating to 90 ℃, carrying out polymerization reaction, and obtaining polybutadiene latex when the butadiene conversion rate is 91%.

Comparative example 2

The allyl polyether monomer of comparative example 2 is compared to that of example 1, except that the ratio of PO: EO is 1: 1.

comparative example PO: EO is 1: 1 the preparation of allyl polyether monomer comprises the following steps: adding 58g of allyl alcohol into a reaction kettle, heating to 100 ℃, stirring, adding 348g of propylene oxide, 264g of ethylene oxide and 1.61g of KOH for polymerization; adding phosphoric acid with the same molar weight as KOH when the conversion rate of the propylene oxide is 99.1 percent, uniformly stirring, removing generated water under the conditions of 110 ℃ and 5Kpa, and obtaining the allyl polyether monomer when the water content of the reactant is 0.04 percent.

The preparation of the butadiene latex in this comparative example differs from example 6 only in that: the allyl polyether prepared in example 1 of example 6 was replaced with the allyl polyether prepared in this comparative example, and the remaining starting materials, experimental conditions and reaction steps were the same as in example 6.

Comparative example 3

The allyl polyether monomer of comparative example 3 is compared to that of example 1, except that: the allyl polyether monomer is free of EO.

The preparation of an allyl polyether monomer without EO of this comparative example includes the following steps: adding 58g of allyl alcohol into a reaction kettle, heating to 100 ℃, stirring, adding 522g of propylene oxide and 1.61g of KOH, and carrying out polymerization reaction; adding phosphoric acid with the same molar weight as KOH when the conversion rate of the propylene oxide is 99.1 percent, uniformly stirring, removing generated water under the conditions of 110 ℃ and 5Kpa, and obtaining the allyl polyether monomer when the water content of the reactant is 0.04 percent.

Examples of the experimentsGel content determination

The gel content was tested as follows: polybutadiene latex was completely dried at a temperature of less than 60 ℃ and 0.2g of a completely dried polybutadiene latex sample was soaked in 50g of toluene to swell, and after swelling for 24 hours at room temperature, toluene was removed by suction, and the remaining sample was dried again and weighed as m.

Calculated according to the following formula: gel content ═ m/0.2 × 100%.

The results of the gel content measurement are shown in Table 3.

TABLE 3 gel content measurement results

	Example 6	Example 7	Example 8	Example 9	Example 10	Comparative example 1	Comparative example 2	Comparative example 3
									Gel content	52	42	33	67	15	82	80	76

As can be seen from Table 3, (1) polybutadiene latex prepared by copolymerization of allyl polyether without EO segment added in comparative example 3, because allyl polyether without EO segment is poor in hydrophilicity, it is embedded in the middle of latex particles, and cannot effectively form polybutadiene molecular chain barrier; (2) PO: EO is 1: 1, because the EO content is too high and the hydrophilicity is too strong, the allyl polyether is easy to dissolve in water and is easy to migrate to water or the surface of latex particles in the polymerization reaction, thereby the contact of polybutadiene molecular chains cannot be effectively prevented, and the gel content is higher; (3) in comparative example 1, any steric-hindrance functional monomer is not added, the monomer concentration in the system is insufficient in the later polymerization stage of the polybutadiene latex, and when the monomer concentration is sufficient in the earlier polymerization stage, the free radicals generated by the initiator are relatively excessive, the excessive free radicals attack the residual double bonds on the molecular chains of the polymerized polybutadiene, and the double bonds between the molecular chains of the polybutadiene are polymerized to generate crosslinking due to the absence of the steric hindrance effect, so that the gel content is increased.

As shown above, when the butadiene conversion rate is 20-70%, an allyl polyether monomer containing n EO segments and m PO segments (wherein n is an integer from 3 to 6, m is an integer from 6 to 18, and m is 2. ltoreq. m: n. ltoreq.6) is added for copolymerization to prepare polybutadiene latex with the gel content of 10-70%, preferably 15-67%.

Examples of the experimentsPreparation and performance detection of ABS resin

It is a conventional technique in the art to agglomerate, graft, agglomerate, filter, dry polybutadiene latex to obtain polymer rubber powder, and then mechanically blend, melt and granulate the polymer rubber powder with styrene acrylonitrile copolymer (SAN resin) to obtain ABS resin, and the specific operation can refer to the book "ABS resin and its application" written in Huangli Ben, etc.

The ABS resin is prepared from polybutadiene latex according to the following method: (1) 1700g of the polybutadiene latexes prepared in examples 6 to 10 and comparative examples 1 to 3 were taken, stirred and added with a 5% acetic acid aqueous solution, when the latex particle size reached 300nm, the addition of the acetic acid aqueous solution was stopped, and a 7% KOH aqueous solution was added to adjust the pH of the latex to 12, and stirred uniformly, to obtain the agglomerated polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3, respectively. (2) 63kg of the agglomerated polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3 were charged into a grafting vessel, respectively, and the temperature was raised to 80 ℃ and then 0.25kg of cumene hydroperoxide, 0.01kg of lactose, 0.00015kg of ferrous sulfate as an initiator, 28kg of styrene, 12kg of acrylonitrile, 0.45kg of TDM0, 0.007kg of sodium pyrophosphate, 0.6kg of potassium oleate and 10kg of deionized water were sequentially added thereto to conduct polymerization, and when the conversion of acrylonitrile was 97%, graft ABS latexes prepared from the polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3 were obtained, respectively. (3) 100kg of the graft ABS latex prepared from the polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3 were taken, respectively, and 4kg of a 5% magnesium sulfate aqueous solution and 1kg of a 5% acetic acid aqueous solution were added thereto, aged for 2 hours, filtered and dried at 80 ℃ until the water content became 1%, to obtain ABS rubber powders prepared from the polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3, respectively. (4) Respectively adding 25kg

ABS rubber powders prepared from the polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3, 75kg of PN118L150 SAN resin, 0.1kg of antioxidant B900, 0.2kg of magnesium stearate and 2kg of N, N-ethylene bisstearamide were kneaded in a high-speed kneader for 5 minutes, and then the mixed materials were melt-pelletized and blended in a twin-screw extruder, followed by pelletization, to obtain ABS resins prepared from the polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3, respectively.

ABS resins prepared from the polybutadiene latexes of examples 6 to 10 and comparative examples 1 to 3 were dried in an oven at 80 ℃ for 4 hours, respectively, and mechanical property tests were carried out, and the specific test results are shown in Table 4.

TABLE 4 mechanical Properties test

As can be seen from Table 4: (1) the notched impact strength of the ABS resins prepared from the polybutadiene latices of examples 6 to 10 was higher than that of the ABS resins prepared from the polybutadiene latices of comparative examples 1 to 3.

(2) The polybutadiene latices of examples 6-10 exhibited increasing notched impact strength as the gel content decreased for the ABS resins prepared separately.

(3) Comparative example 1 No allyl polyether of the present invention was added and the polybutadiene latex gel content reached 82%, and the ABS resin prepared using the same had an impact strength as low as 20KJ/m²In comparative example 2, the allyl polyether added in the allyl polyether chain segment has higher EO content, which causes the allyl polyether to have too strong hydrophilicity, most of the allyl polyether is dissolved in water and can not be polymerized in latex particles, thereby causing the polybutadiene latex to have higher gel content, and the prepared ABS resin has poorer impact strength which is 21KJ/m²However, the impact strength was somewhat improved relative to the ABS resin of comparative example 1, in which no allyl polyether was added. The allyl polyether segment added in comparative example 3 contains only hydrophobesThe PO chain segment of water causes the allyl polyether to have poor water solubility, most of the allyl polyether is embedded into the latex particles and can not obstruct the cross-linking reaction of the polybutadiene chain segment at the outer layer of the latex particles, thereby causing the polybutadiene latex to have higher gel content, and the impact strength of the prepared ABS resin is 22KJ/m²Higher than the ABS resin obtained in comparative example 1 in which no allyl polyether was added and the ABS resin obtained in comparative example 2 in which only a small amount of allyl polyether was polymerized to the polybutadiene latex.

As shown above, the low gel content polybutadiene latex of the present invention can effectively improve the impact resistance of ABS resin.

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.

Claims

1. A method for preparing polybutadiene latex with low gel content is characterized by comprising the following steps:

respectively adding 1-5 parts by weight of emulsifier, 100 parts by weight of butadiene, 0.1-1 part by weight of neutralizer, 0.1-0.5 part by weight of initiator and 100-150 parts by weight of water into a reaction vessel, and heating to 60-90 ℃, preferably 65-85 ℃ for polymerization reaction;

and when the butadiene conversion rate is more than or equal to 20% and less than or equal to 70%, adding allyl polyether for copolymerization reaction, and obtaining polybutadiene latex when the butadiene conversion rate is more than or equal to 90%.

2. The method for preparing polybutadiene latex with low gel content according to claim 1, wherein the allyl polyether is added in an amount of 1-5 parts by weight.

3. The process for the preparation of polybutadiene latex with low gel content according to claim 1 or 2, wherein,

the allyl polyether contains n EO chain segments and m PO chain segments,

wherein n is an integer from 3 to 6, m is an integer from 6 to 18, m is not less than 2: n is less than or equal to 6.

4. The process for the preparation of polybutadiene latex with low gel content, according to any one of claims 1 to 3, characterized in that,

the emulsifier is at least one of potassium oleate, sodium dodecyl sulfate and disproportionated potassium abietate.

5. The process for the preparation of polybutadiene latex with low gel content according to any one of claims 1 to 4, wherein,

the neutralizing agent is at least one selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide, and is preferably selected from potassium carbonate and/or potassium hydroxide.

6. The process for the preparation of polybutadiene latex with low gel content, according to any one of claims 1 to 5, wherein,

the initiator is a peroxide initiator, preferably at least one of potassium persulfate, sodium persulfate and ammonium persulfate.

7. Process for the preparation of a polybutadiene latex with a low gel content, according to any one of the claims 1-6, characterized in that said allyl polyether is prepared by means of a process comprising the following steps:

adding 58 parts by weight of allyl alcohol into a reaction vessel, heating to 100 ℃ and 130 ℃, adding 58m parts by weight of propylene oxide, 44n parts by weight of ethylene oxide and KOH under stirring for polymerization, wherein the addition amount of KOH is 0.3-1% based on 100% of the total weight of the allyl alcohol, the propylene oxide and the ethylene oxide;

8. Polybutadiene latex obtained by the process according to any one of claims 1 to 7.

9. Polybutadiene latex according to claim 8, characterized in that it has a gel content ranging from 10% to 70%, preferably from 15% to 67%.

10. An ABS resin, characterized by being made of the low gel content polybutadiene latex of claim 8 or 9.