Accelerator dispersion masterbatch and method of making

Abstract

The application discloses a kind of accelerator dispersion master batch and preparation method thereof, it is related to rubber auxiliary field, to improve the stable performance of accelerator dispersion master batch.The accelerator dispersion master batch includes 25-40 weight powder carrier and 60-75 weight modified accelerator.The carrier includes the oil-extended ternary ethylene-propylene rubber, non-oil-extended ternary ethylene-propylene rubber, ethylene-vinyl acetate copolymer and rosin in a weight ratio of (20-60):(40-80):(10-40):(10-40), and the modified accelerator includes the accelerator and rosin glyceride in a weight ratio of (70-80):(20-30).The accelerator dispersion master batch in the application does not occur blooming problem within two years, and the pulverization rate is low, and the stability is high.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of rubber auxiliaries, in particular to a promoter dispersion master batch and a preparation method thereof. BACKGROUND

[0002] Traditional rubber promoters are mostly powdery substances, which are easy to cause dust pollution during the production of rubber products, and even cause safety hazards in severe cases. In addition, the compatibility of rubber promoters with rubber is relatively poor, and it is difficult to uniformly disperse in rubber in a short time, resulting in quality problems of rubber products.

[0003] In order to improve the workshop environment, at present, the promoter is usually pre-dispersed in ethylene-propylene-diene rubber in the related art, and then granulated to prepare a promoter dispersion master batch, which is used to replace the traditional powdery rubber promoter to improve the dust pollution problem in the processing of rubber products.

[0004] Among them, the rubber promoter is pre-dispersed in ethylene-propylene-diene rubber, which is equivalent to prolonging the dispersion time of the rubber promoter, and can also improve the problem of uneven dispersion of the rubber promoter in the rubber to a certain extent. However, due to the low cohesive energy and poor mutual adhesion of ethylene-propylene-diene rubber, the promoter dispersion master batch is easy to fall off from the ethylene-propylene-diene rubber after long-term storage, and has the problem of poor stability. SUMMARY

[0005] In order to improve the poor adhesion between the promoter and the ethylene-propylene-diene rubber in the promoter dispersion master batch, and the problem that the promoter on the promoter dispersion master batch is easy to fall off after long-term storage, the present application provides a promoter dispersion master batch and a preparation method thereof.

[0006] In a first aspect, the present application provides a promoter dispersion master batch using the following technical scheme:

[0007] A promoter dispersion master batch comprises the following raw materials by weight:

[0008] Carrier: 25-40 parts

[0009] Modified promoter: 60-75 parts

[0010] The carrier comprises oil-extended ethylene-propylene-diene rubber, non-oil-extended ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and rosin, and the weight ratio of the oil-extended ethylene-propylene-diene rubber, non-oil-extended ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and rosin is (20-60):(40-80):(10-40):(10-40).

[0011] The modified promoter comprises a promoter and a rosin glyceride, and the weight ratio of the promoter and the rosin glyceride is (70-80):(20-30).

[0012] The pre-modification of the accelerator by rosin glyceride is beneficial to improve the dispersibility of the accelerator in the carrier, and also beneficial to improve the compatibility and adhesion strength of the accelerator and the carrier, and can effectively delay the occurrence of the blooming problem of the accelerator dispersion master batch. The carrier uses a composition of oil-extended ternary ethylene-propylene rubber, non-oil-extended ternary ethylene-propylene rubber, ethylene-vinyl acetate copolymer and rosin. Specifically, the addition of a specific ratio of oil-extended ternary ethylene-propylene rubber in the carrier can prevent the rubber from remaining on the screw, which causes the problem that the rubber cannot be uniformly mixed, improve the processing performance, and improve the dispersion effect of the modified accelerator in the carrier, and promote the adhesion strength of the modified accelerator and the carrier. However, the oil-extended ternary ethylene-propylene rubber should not be added in excess, otherwise it is easy to cause the problem that the rubber slips and cannot be uniformly mixed, thereby reducing the adhesion strength of the modified accelerator and the carrier, and is not conducive to improving the stability of the accelerator dispersion master batch. The addition of a specific ratio of ethylene-vinyl acetate copolymer and rosin in the carrier can further improve the adhesion strength between the accelerator and the ternary ethylene-propylene rubber, thereby preventing the accelerator from falling off during storage, and plays a key role in improving the stability of the accelerator dispersion master batch.

[0013] Optionally, the weight ratio of the oil-extended ternary ethylene-propylene rubber, the non-oil-extended ternary ethylene-propylene rubber, the ethylene-vinyl acetate copolymer and the rosin is (30-40):(60-70):(30-40):(10-20).

[0014] When the weight ratio of the oil-extended ternary ethylene-propylene rubber, the non-oil-extended ternary ethylene-propylene rubber, the ethylene-vinyl acetate copolymer and the rosin is within the above range, the uniform dispersion performance of the accelerator in the carrier is further improved, and the problem of easy falling off of the accelerator is further improved, thereby further improving the stability of the accelerator dispersion master batch.

[0015] Optionally, the weight ratio of the oil-extended ternary ethylene-propylene rubber, the non-oil-extended ternary ethylene-propylene rubber, the ethylene-vinyl acetate copolymer and the rosin is 35:65:35:15.

[0016] When the weight ratio of the oil-extended ternary ethylene-propylene rubber, the non-oil-extended ternary ethylene-propylene rubber, the ethylene-vinyl acetate copolymer and the rosin is 35:65:35:15, the uniform dispersion performance of the accelerator is the best, and the stability of the accelerator dispersion master batch is further improved.

[0017] Optionally, the oil-extended ternary ethylene-propylene rubber includes non-oil-extended ternary ethylene-propylene rubber and filling oil, and the weight ratio of the non-oil-extended ternary ethylene-propylene rubber and the filling oil is (60-70):(30-40).

[0018] Optionally, the melt index of the ethylene-vinyl acetate copolymer is 3-4 g / 10 min.

[0019] When the melt index of the ethylene-vinyl acetate copolymer is within the range, the compatibility between the ethylene-vinyl acetate copolymer and the ethylene-propylene-diene rubber is further improved, the uniform dispersion of the ethylene-vinyl acetate copolymer in the ethylene-propylene-diene rubber is further improved, and the adhesion between the accelerator and the carrier is improved.

[0020] Optionally, the ethylene-vinyl acetate copolymer is a maleic anhydride grafted ethylene-vinyl acetate copolymer.

[0021] The maleic anhydride grafted ethylene-vinyl acetate copolymer has excellent compatibility with the ethylene-propylene-diene rubber. When the ethylene-vinyl acetate copolymer is a maleic anhydride grafted ethylene-vinyl acetate copolymer, the maleic anhydride grafted ethylene-vinyl acetate copolymer can be uniformly dispersed in the ethylene-propylene-diene rubber, which further improves the adhesion between the accelerator and the carrier and further improves the stability of the accelerator dispersion master batch.

[0022] Optionally, the accelerator is at least one of zinc dimethyl dithiocarbamate, tetramethyl thiuram disulfide, and 2-mercaptobenzothiazole.

[0023] In a second aspect, the application provides a preparation method of an accelerator dispersion master batch, which adopts the following technical scheme:

[0024] The preparation method of the accelerator dispersion master batch comprises the following steps:

[0025] The oil-extended ethylene-propylene-diene rubber, the non-oil-extended ethylene-propylene-diene rubber, the ethylene-vinyl acetate copolymer, and the rosin are uniformly mixed according to a ratio to obtain a carrier.

[0026] The accelerator and the rosin glyceride are uniformly mixed according to a ratio, and then melted and extruded at 70-110°C, and then granulated to obtain a modified accelerator. The carrier and the modified accelerator are uniformly mixed to obtain a premix.

[0027] The premix is melted and extruded at 170-200°C, and then granulated to obtain the accelerator dispersion master batch.

[0028] The accelerator is pre-modified by the rosin glyceride to obtain a modified accelerator, and then the modified accelerator and the carrier are mixed, melted, and extruded and granulated to prepare the accelerator dispersion master batch, which is beneficial to improving the dispersion of the accelerator in the carrier, improving the compatibility and adhesion between the accelerator and the carrier, and effectively delaying the occurrence of the blooming problem and the accelerator shedding problem of the accelerator dispersion master batch.

[0029] Preferably, the melting and extrusion temperature of the modified accelerator is controlled at 75-90°C, and the melting and extrusion temperature of the accelerator dispersion master batch is controlled at 180-200°C.

[0030] Optionally, the melt extrusion of the modified accelerator is performed in a twin-screw extruder, screw of which is sequentially divided into conveying section, melting section, plasticizing section and discharging section along the conveying direction of the material, the temperature of the conveying section is 75-80 DEG C, the temperature of the melting section is 80-85 DEG C, the temperature of the plasticizing section is 80-85 DEG C, and the temperature of the discharging section is 85-90 DEG C.

[0031] When the modified accelerator is prepared according to the above method, the accelerator can be uniformly dispersed in the colophony glyceride, and the colophony glyceride is not lost due to volatilization, so that the modified accelerator coated by the colophony glyceride can be obtained, and the compatibility and adhesion of the modified accelerator and the carrier can be improved.

[0032] Optionally, the melt extrusion of the accelerator dispersion master batch is performed in a twin-screw extruder, screw of which is sequentially divided into conveying section, melting section, plasticizing section and discharging section along the conveying direction of the material, the temperature of the conveying section is 180-185 DEG C, the temperature of the melting section is 185-190 DEG C, the temperature of the plasticizing section is 190-195 DEG C, and the temperature of the discharging section is 195-200 DEG C.

[0033] When the accelerator dispersion master batch is prepared according to the above method, the components can be uniformly dispersed, and the rubber is not locally degraded, so that the production stability of the accelerator dispersion master batch can be improved.

[0034] In summary, the technical scheme of the present application at least has the following beneficial effects:

[0035] (1) The accelerator is pre-modified by the colophony glyceride, which is beneficial to improve the dispersibility of the accelerator in the carrier, and is beneficial to improve the compatibility and adhesion of the accelerator and the carrier, and can effectively delay the occurrence of the blooming problem of the accelerator dispersion master batch.

[0036] (2) The carrier in the present application includes oil-extended EPDM, non-oil-extended EPDM, ethylene-vinyl acetate copolymer and colophony, when the weight ratio of the oil-extended EPDM, the non-oil-extended EPDM, the ethylene-vinyl acetate copolymer and the colophony is in the range of (20-60):(40-80):(10-40):(10-40), the dispersing effect of the modified accelerator in the carrier can be effectively improved, the adhesion between the modified accelerator and the carrier can be further improved, and the stability of the accelerator dispersion master batch can be effectively improved.

[0037] (3) When the ethylene-vinyl acetate copolymer is selected as the maleic anhydride grafted ethylene-vinyl acetate copolymer, the maleic anhydride grafted ethylene-vinyl acetate copolymer has more excellent compatibility with the EPDM, and the maleic anhydride grafted ethylene-vinyl acetate copolymer can be uniformly dispersed in the EPDM, which further promotes the adhesion of the accelerator to the carrier. DETAILED DESCRIPTION

[0038] The application will be further described in detail below in combination with specific experiments.

[0039] EMBODIMENT

[0040] EMBODIMENT 1

[0041] A kind of accelerator dispersion master batch, including 25kg carrier and 75kg modified accelerator.

[0042] The carrier includes 20kg oil-extended EPDM, 80kg non-oil-extended EPDM with the trademark 4045 of Mitsubishi Chemical, 20kg ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min and 30kg rosin by raw material.

[0043] The oil-extended EPDM is obtained by mixing non-oil-extended EPDM with the trademark 4045 of Mitsubishi Chemical and naphthenic oil at a weight ratio of 65:35.

[0044] The modified accelerator includes 70kg zinc dimethyl dithiocarbamate and 30kg rosin glyceride by raw material.

[0045] The preparation method of the accelerator dispersion master batch of the embodiment includes the following steps:

[0046] The oil-extended EPDM, non-oil-extended EPDM, ethylene-vinyl acetate copolymer and rosin are uniformly mixed according to the ratio to obtain the carrier;

[0047] The zinc dimethyl dithiocarbamate and rosin glyceride are uniformly mixed according to the ratio, and then are put into a twin-screw extruder for melt extrusion, granulation to obtain the modified accelerator; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75℃, the temperature of the melting section is 80℃, the temperature of the plasticizing section is 85℃, and the temperature of the discharge section is 90℃;

[0048] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0049] The premix is put into a twin-screw extruder for melt extrusion, and granulation to obtain the accelerator dispersion master batch; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180℃, the temperature of the melting section is 185℃, the temperature of the plasticizing section is 195℃, and the temperature of the discharge section is 200℃.

[0050] Example 2

[0051] An accelerator dispersion master batch, comprising 30 kg of a carrier and 70 kg of a modified accelerator.

[0052] The carrier comprises, based on the raw materials, 20 kg of an oil-extended ternary ethylene-propylene-diene rubber, 80 kg of a non-oil-extended ternary ethylene-propylene-diene rubber with a brand of 4045 from Mitsui Chemical, 20 kg of an ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 30 kg of rosin.

[0053] The oil-extended ternary ethylene-propylene-diene rubber is obtained by mixing the non-oil-extended ternary ethylene-propylene-diene rubber with a brand of 4045 from Mitsui Chemical and naphthenic oil at a weight ratio of 65:35.

[0054] The modified accelerator comprises, based on the raw materials, 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin glyceride.

[0055] The preparation method of the accelerator dispersion master batch of the present embodiment comprises the following steps:

[0056] The oil-extended ternary ethylene-propylene-diene rubber, the non-oil-extended ternary ethylene-propylene-diene rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain the carrier;

[0057] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then put into a twin-screw extruder for melt extrusion and granulation to obtain the modified accelerator; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75℃, the temperature of the melting section is 80℃, the temperature of the plasticizing section is 85℃, and the temperature of the discharge section is 90℃.

[0058] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0059] The premix is put into a twin-screw extruder for melt extrusion, and granulation to obtain the accelerator dispersion master batch; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180℃, the temperature of the melting section is 185℃, the temperature of the plasticizing section is 195℃, and the temperature of the discharge section is 200℃.

[0060] Example 3

[0061] A promoter dispersion master batch, comprising 40 kg of a carrier and 60 kg of a modified promoter.

[0062] The carrier comprises, based on raw materials, 20 kg of oil-extended ethylene-propylene-diene rubber, 80 kg of non-oil-extended ethylene-propylene-diene rubber with a trademark of 4045 of Mitsui Chemical, 20 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 30 kg of rosin.

[0063] The oil-extended ethylene-propylene-diene rubber is obtained by mixing non-oil-extended ethylene-propylene-diene rubber with a trademark of 4045 of Mitsui Chemical and naphthenic oil at a weight ratio of 65:35.

[0064] The modified promoter comprises, based on raw materials, 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin glyceride.

[0065] The preparation method of the promoter dispersion master batch in the embodiment comprises the following steps:

[0066] The oil-extended ethylene-propylene-diene rubber, the non-oil-extended ethylene-propylene-diene rubber, the ethylene-vinyl acetate copolymer, and the rosin are uniformly mixed according to the proportion to obtain the carrier;

[0067] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are fed into a double-screw extruder for melt extrusion and granulation to obtain the modified promoter; the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section, and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75℃, the temperature of the melting section is 80℃, the temperature of the plasticizing section is 85℃, and the temperature of the discharge section is 90℃.

[0068] The carrier and the modified promoter are uniformly mixed to obtain a premix;

[0069] The premix is fed into a double-screw extruder for melt extrusion and granulation to obtain the promoter dispersion master batch; the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section, and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180℃, the temperature of the melting section is 185℃, the temperature of the plasticizing section is 195℃, and the temperature of the discharge section is 200℃.

[0070] Example 4

[0071] A promoter dispersion master batch, comprising 30 kg of a carrier and 70 kg of a modified promoter.

[0072] The carrier comprises, based on raw materials, 25 kg of oil-extended ethylene-propylene-diene rubber, 75 kg of non-oil-extended ethylene-propylene-diene rubber with a trademark of 4045 of Mitsui Chemical, 20 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 30 kg of rosin.

[0073] The oil-extended EPDM rubber is obtained by mixing non-oil-extended EPDM rubber with the trade mark 4045 of Mitsui Chemical and naphthenic oil at a weight ratio of 65:35.

[0074] According to the raw materials, the modified accelerator comprises 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin glyceride.

[0075] The preparation method of the accelerator dispersion master batch in the embodiment comprises the following steps:

[0076] The oil-extended EPDM rubber, the non-oil-extended EPDM rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain a carrier;

[0077] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are put into a double-screw extruder for melt extrusion and granulation to obtain the modified accelerator; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75 ℃, the temperature of the melting section is 80 ℃, the temperature of the plasticizing section is 85 ℃, and the temperature of the discharge section is 90 ℃.

[0078] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0079] The premix is put into a double-screw extruder for melt extrusion and granulation to obtain the accelerator dispersion master batch; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180 ℃, the temperature of the melting section is 185 ℃, the temperature of the plasticizing section is 195 ℃, and the temperature of the discharge section is 200 ℃.

[0080] Example 5

[0081] An accelerator dispersion master batch comprises 30 kg of a carrier and 70 kg of a modified accelerator.

[0082] According to the raw materials, the carrier comprises 30 kg of oil-extended EPDM rubber, 70 kg of non-oil-extended EPDM rubber with the trade mark 4045 of Mitsui Chemical, 40 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min and 10 kg of rosin.

[0083] The oil-extended EPDM rubber is obtained by mixing non-oil-extended EPDM rubber with the trade mark 4045 of Mitsui Chemical and naphthenic oil at a weight ratio of 65:35.

[0084] According to the raw materials, the modified accelerator comprises 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin glyceride.

[0085] The preparation method of the accelerator dispersion master batch in the embodiment comprises the following steps:

[0086] The oil-extended EPDM rubber, the non-oil-extended EPDM rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain a carrier;

[0087] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are put into a twin-screw extruder for melt extrusion and granulation to obtain the modified accelerator; the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75 DEG C, the temperature of the melting section is 80 DEG C, the temperature of the plasticizing section is 85 DEG C, and the temperature of the discharge section is 90 DEG C;

[0088] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0089] The premix is put into a twin-screw extruder for melt extrusion and granulation to obtain the accelerator dispersion master batch; the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180 DEG C, the temperature of the melting section is 185 DEG C, the temperature of the plasticizing section is 195 DEG C, and the temperature of the discharge section is 200 DEG C.

[0090] Example 6

[0091] An accelerator dispersion master batch, comprising 30 kg of the carrier and 70 kg of the modified accelerator.

[0092] According to the raw materials, the carrier comprises 35 kg of the oil-extended EPDM rubber, 65 kg of the non-oil-extended EPDM rubber of the trademark 4045 of Mitsui Chemical, 35 kg of the ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 15 kg of the rosin.

[0093] The oil-extended EPDM rubber is obtained by mixing the non-oil-extended EPDM rubber of the trademark 4045 of Mitsui Chemical with naphthenic oil according to a weight ratio of 65:35.

[0094] According to the raw materials, the modified accelerator comprises 70 kg of the zinc dimethyl dithiocarbamate and 30 kg of the rosin glyceride.

[0095] The preparation method of the accelerator dispersion master batch of the embodiment comprises the following steps:

[0096] The oil-extended EPDM rubber, the non-oil-extended EPDM rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain a carrier;

[0097] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are put into a double-screw extruder for melt extrusion and granulation to obtain a modified accelerator; wherein, the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75 DEG C, the temperature of the melting section is 80 DEG C, the temperature of the plasticizing section is 85 DEG C, and the temperature of the discharge section is 90 DEG C.

[0098] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0099] The premix is put into a double-screw extruder for melt extrusion and granulation to obtain an accelerator dispersion master batch; wherein, the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180 DEG C, the temperature of the melting section is 185 DEG C, the temperature of the plasticizing section is 195 DEG C, and the temperature of the discharge section is 200 DEG C.

[0100] Example 7

[0101] An accelerator dispersion master batch, comprising 30 kg of a carrier and 70 kg of a modified accelerator.

[0102] According to the raw materials, the carrier comprises 40 kg of an oil-extended ternary ethylene-propylene-diene rubber, 60 kg of a non-oil-extended ternary ethylene-propylene-diene rubber with a brand of 4045 from Mitsui Chemical, 30 kg of an ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 20 kg of rosin.

[0103] The oil-extended ternary ethylene-propylene-diene rubber is obtained by mixing the non-oil-extended ternary ethylene-propylene-diene rubber with a brand of 4045 from Mitsui Chemical and naphthenic oil according to a weight ratio of 65:35.

[0104] According to the raw materials, the modified accelerator comprises 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin glyceride.

[0105] The preparation method of the accelerator dispersion master batch of the embodiment comprises the following steps:

[0106] The oil-extended ternary ethylene-propylene-diene rubber, the non-oil-extended ternary ethylene-propylene-diene rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain a carrier;

[0107] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are put into a double-screw extruder for melt extrusion and granulation to obtain a modified accelerator; wherein, the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75 DEG C, the temperature of the melting section is 80 DEG C, the temperature of the plasticizing section is 85 DEG C, and the temperature of the discharge section is 90 DEG C.

[0108] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0109] The premix is fed into a twin-screw extruder for melt extrusion, and granulation to obtain the accelerator dispersion master batch; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180℃, the temperature of the melting section is 185℃, the temperature of the plasticizing section is 195℃, and the temperature of the discharge section is 200℃.

[0110] Example 8

[0111] An accelerator dispersion master batch, comprising 30 kg of a carrier and 70 kg of a modified accelerator.

[0112] The carrier comprises, based on the raw materials, 50 kg of oil-extended ethylene-propylene-diene rubber, 50 kg of non-oil-extended ethylene-propylene-diene rubber of the brand 4045 of Mitsui Chemical, 20 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 30 kg of rosin.

[0113] The oil-extended ethylene-propylene-diene rubber is obtained by mixing the non-oil-extended ethylene-propylene-diene rubber of the brand 4045 of Mitsui Chemical with naphthenic oil at a weight ratio of 65:35.

[0114] The modified accelerator comprises, based on the raw materials, 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin glyceride.

[0115] The preparation method of the accelerator dispersion master batch of the present example comprises the following steps:

[0116] The oil-extended ethylene-propylene-diene rubber, the non-oil-extended ethylene-propylene-diene rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain the carrier;

[0117] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then fed into a twin-screw extruder for melt extrusion and granulation to obtain the modified accelerator; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75℃, the temperature of the melting section is 80℃, the temperature of the plasticizing section is 85℃, and the temperature of the discharge section is 90℃.

[0118] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0119] The premix is fed into a twin-screw extruder for melt extrusion, and granulation to obtain the accelerator dispersion master batch; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180℃, the temperature of the melting section is 185℃, the temperature of the plasticizing section is 195℃, and the temperature of the discharge section is 200℃.

[0120] Example 9

[0121] A promoter dispersion master batch, comprising 30 kg of a carrier and 70 kg of a modified promoter.

[0122] The carrier comprises, by raw material, 60 kg of oil-extended terpolymer ethylene-propylene rubber, 40 kg of non-oil-extended terpolymer ethylene-propylene rubber of the type 4045 of Mitsui Chemical, 10 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 40 kg of rosin.

[0123] The oil-extended terpolymer ethylene-propylene rubber is obtained by mixing the non-oil-extended terpolymer ethylene-propylene rubber of the type 4045 of Mitsui Chemical with naphthenic oil at a weight ratio of 65:35.

[0124] The modified promoter comprises, by raw material, 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin glyceride.

[0125] The preparation method of the promoter dispersion master batch in the embodiment comprises the following steps:

[0126] The oil-extended terpolymer ethylene-propylene rubber, the non-oil-extended terpolymer ethylene-propylene rubber, the ethylene-vinyl acetate copolymer, and the rosin are uniformly mixed according to the proportion to obtain the carrier;

[0127] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are fed into a double-screw extruder for melt extrusion and granulation to obtain the modified promoter; the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section, and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75°C, the temperature of the melting section is 80°C, the temperature of the plasticizing section is 85°C, and the temperature of the discharge section is 90°C.

[0128] The carrier and the modified promoter are uniformly mixed to obtain a premix;

[0129] The premix is fed into a double-screw extruder for melt extrusion and granulation to obtain the promoter dispersion master batch; the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section, and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180°C, the temperature of the melting section is 185°C, the temperature of the plasticizing section is 195°C, and the temperature of the discharge section is 200°C.

[0130] Example 10

[0131] A promoter dispersion master batch, comprising 30 kg of a carrier and 70 kg of a modified promoter.

[0132] The carrier comprises, by raw material, 60 kg of oil-extended terpolymer ethylene-propylene rubber, 40 kg of non-oil-extended terpolymer ethylene-propylene rubber of the type 4045 of Mitsui Chemical, 10 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 40 kg of rosin.

[0133] The oil-extended EPDM rubber is obtained by mixing non-oil-extended EPDM rubber with the trade mark 4045 of Mitsui Chemical and naphthenic oil at a weight ratio of 65:35.

[0134] According to the raw materials, the modified accelerator comprises 75 kg of zinc dimethyl dithiocarbamate and 25 kg of rosin glyceride.

[0135] The preparation method of the accelerator dispersion master batch in the embodiment comprises the following steps:

[0136] The oil-extended EPDM rubber, the non-oil-extended EPDM rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain a carrier.

[0137] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are put into a double-screw extruder for melt extrusion and granulation to obtain the modified accelerator; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 75 ℃, the temperature of the melting section is 80 ℃, the temperature of the plasticizing section is 85 ℃, and the temperature of the discharge section is 90 ℃.

[0138] The carrier and the modified accelerator are uniformly mixed to obtain a premix.

[0139] The premix is put into a double-screw extruder for melt extrusion and granulation to obtain the accelerator dispersion master batch; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180 ℃, the temperature of the melting section is 185 ℃, the temperature of the plasticizing section is 195 ℃, and the temperature of the discharge section is 200 ℃.

[0140] Example 11

[0141] An accelerator dispersion master batch comprises 30 kg of a carrier and 70 kg of a modified accelerator.

[0142] According to the raw materials, the carrier comprises 35 kg of oil-extended EPDM rubber, 65 kg of non-oil-extended EPDM rubber with the trade mark 4045 of Mitsui Chemical, 35 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 15 kg of rosin.

[0143] The oil-extended EPDM rubber is obtained by mixing non-oil-extended EPDM rubber with the trade mark 4045 of Mitsui Chemical and naphthenic oil at a weight ratio of 65:35.

[0144] According to the raw materials, the modified accelerator comprises 80 kg of zinc dimethyl dithiocarbamate and 20 kg of rosin glyceride.

[0145] The preparation method of the accelerator dispersion master batch in the embodiment comprises the following steps:

[0146] The oil-extended EPDM rubber, the non-oil-extended EPDM rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain a carrier;

[0147] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to the proportion, and then are put into a double-screw extruder for melt extrusion and granulation to obtain a modified accelerator; the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 75 DEG C, the temperature of the melting section is 80 DEG C, the temperature of the plasticizing section is 85 DEG C, and the temperature of the discharging section is 90 DEG C;

[0148] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0149] The premix is put into a double-screw extruder for melt extrusion and granulation to obtain an accelerator dispersion master batch; the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 180 DEG C, the temperature of the melting section is 185 DEG C, the temperature of the plasticizing section is 195 DEG C, and the temperature of the discharging section is 200 DEG C.

[0150] Example 12

[0151] An accelerator dispersion master batch, comprising 30 kg of a carrier and 70 kg of a modified accelerator.

[0152] According to the raw materials, the carrier comprises 35 kg of oil-extended EPDM rubber, 65 kg of non-oil-extended EPDM rubber of the 4045 brand of Mitsui Chemical, 35 kg of maleic anhydride grafted ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 15 kg of rosin. The maleic anhydride grafted ethylene-vinyl acetate copolymer is from Arkema, and the brand is 18211.

[0153] The oil-extended EPDM rubber is obtained by mixing the non-oil-extended EPDM rubber of the 4045 brand of Mitsui Chemical with naphthenic oil according to a weight ratio of 65:35.

[0154] According to the raw materials, the modified accelerator comprises 75 kg of zinc dimethyl dithiocarbamate and 25 kg of rosin glyceride.

[0155] The preparation method of the accelerator dispersion master batch of the embodiment comprises the following steps:

[0156] The oil-extended EPDM rubber, the non-oil-extended EPDM rubber, the maleic anhydride grafted ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportion to obtain a carrier;

[0157] The zinc dimethyl dithiocarbamate and the rosin glyceride are uniformly mixed according to a ratio, and then are put into a double-screw extruder to be melt-extruded and granulated to obtain a modified accelerator; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 75℃, the temperature of the melting section is 80℃, the temperature of the plasticizing section is 85℃, and the temperature of the discharging section is 90℃.

[0158] The carrier and the modified accelerator are uniformly mixed to obtain a premix;

[0159] The premix is put into a double-screw extruder to be melt-extruded and granulated to obtain an accelerator dispersion master batch; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 180℃, the temperature of the melting section is 185℃, the temperature of the plasticizing section is 195℃, and the temperature of the discharging section is 200℃.

[0160] Comparative Example 1

[0161] Comparative Example 1

[0162] An accelerator dispersion master batch, which is different from that of Example 2 in that the carrier composition is different.

[0163] In the present comparative example, the carrier includes 100 kg of non-oil-filled ternary ethylene-propylene rubber of the 4045 brand of Mitsui Chemical, 20 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 30 kg of rosin.

[0164] Comparative Example 2

[0165] An accelerator dispersion master batch, which is different from that of Example 2 in that the carrier composition is different.

[0166] In the present comparative example, the carrier includes 100 kg of non-oil-filled ternary ethylene-propylene rubber of the 4045 brand of Mitsui Chemical, 20 kg of ethylene-vinyl acetate copolymer with a melt index of 3.5 g / 10 min, and 30 kg of rosin.

[0167] Comparative Example 3

[0168] An accelerator dispersion master batch, which is different from that of Example 2 in that the carrier composition is different.

[0169] In the present comparative example, the carrier includes 20 kg of non-oil-filled ternary ethylene-propylene rubber of the 4045 brand of Mitsui Chemical, 80 kg of non-oil-filled ternary ethylene-propylene rubber of the 4045 brand of Mitsui Chemical, and 50 kg of rosin.

[0170] Comparative Example 4

[0171] An accelerator dispersion master batch, which is different from that of Example 2 in that the carrier composition is different.

[0172] In the present comparative example, the carrier comprises 20 kg of oil-extended ethylene-propylene-diene rubber, 80 kg of non-oil-extended ethylene-propylene-diene rubber of the brand 4045 of Mitsui Chemical, 50 kg of ethylene-vinyl acetate copolymer having a melt index of 3.5 g / 10 min.

[0173] Comparative Example 5

[0174] A promoter dispersion master batch, which is different from Example 2 in that the carrier composition is different.

[0175] The carrier comprises 5 kg of oil-extended ethylene-propylene-diene rubber, 95 kg of non-oil-extended ethylene-propylene-diene rubber of the brand 4045 of Mitsui Chemical, 5 kg of ethylene-vinyl acetate copolymer having a melt index of 3.5 g / 10 min, and 45 kg of rosin.

[0176] Comparative Example 6

[0177] A promoter dispersion master batch, which is different from Example 2 in that the modified promoter is replaced by zinc dimethyl dithiocarbamate.

[0178] In the present comparative example, the preparation method of the promoter dispersion master batch comprises the following steps:

[0179] The oil-extended ethylene-propylene-diene rubber, the non-oil-extended ethylene-propylene-diene rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportions to obtain a carrier;

[0180] The carrier and the zinc dimethyl dithiocarbamate are uniformly mixed to obtain a premix;

[0181] The premix is fed into a twin-screw extruder for melt extrusion and granulation to obtain a promoter dispersion master batch; wherein the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharge section along the conveying direction of the material, the temperature of the conveying section is 180°C, the temperature of the melting section is 185°C, the temperature of the plasticizing section is 195°C, and the temperature of the discharge section is 200°C.

[0182] Comparative Example 7

[0183] A promoter dispersion master batch, which is different from Example 2 in that:

[0184] In the present comparative example, the modified promoter comprises 70 kg of zinc dimethyl dithiocarbamate and 30 kg of rosin.

[0185] In the present comparative example, the preparation method of the promoter dispersion master batch comprises the following steps:

[0186] The oil-extended ethylene-propylene-diene rubber, the non-oil-extended ethylene-propylene-diene rubber, the ethylene-vinyl acetate copolymer and the rosin are uniformly mixed according to the proportions to obtain a carrier;

[0187] The zinc dimethyl dithiocarbamate and the rosin are uniformly mixed according to a ratio, and then are put into a double-screw extruder to melt extrude and granulate, so as to obtain a modified accelerator; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 115°C, the temperature of the melting section is 120°C, the temperature of the plasticizing section is 125°C, and the temperature of the discharging section is 130°C.

[0188] The carrier and the modified accelerator are uniformly mixed to obtain a premix.

[0189] The premix is put into a double-screw extruder to melt extrude and granulate, so as to obtain an accelerator dispersion master batch; wherein the screw of the double-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 180°C, the temperature of the melting section is 185°C, the temperature of the plasticizing section is 195°C, and the temperature of the discharging section is 200°C.

[0190] Performance detection test

[0191] 1. Powder content: the accelerator dispersion master batch is passed through a 40-mesh sieve, and the accelerator dispersion master batch that can pass through the 40-mesh sieve is regarded as powder.

[0192] 2. Frosting condition: whether frost-like substances are precipitated on the surface of the accelerator dispersion master batch is observed with the naked eye.

[0193] Table 1 Stability detection of accelerator dispersion master batch

[0194]

[0195] In combination with Example 2 and Comparative Examples 1-4 and in combination with the data in Table 1, it can be known that the four of the oil-extended ternary ethylene-propylene rubber, the non-oil-extended ternary ethylene-propylene rubber, the ethylene-vinyl acetate copolymer and the rosin in the carrier have a synergistic effect on improving the stability of the accelerator dispersion master batch, and are indispensable.

[0196] In combination with Examples 2, 4-9 and Comparative Example 5 and in combination with the data in Table 1, it can be known that when the weight ratio of the four of the oil-extended ternary ethylene-propylene rubber, the non-oil-extended ternary ethylene-propylene rubber, the ethylene-vinyl acetate copolymer and the rosin in the carrier is not within the range of (20-60):(40-80):(10-40):(10-40), the powder content of the accelerator dispersion master batch significantly increases with the extension of time. The reason may be that the accelerator dispersion master batch is prone to fall off, which causes the powder content to increase after the accelerator dispersion master batch is stored for a long time, and the reason may also be that the accelerator dispersion master batch itself is aged and cracked and pulverized, which causes the powder content of the accelerator dispersion master batch to increase.

[0197] In combination with Example 2 and Comparative Examples 6-7 and in combination with the data in Table 1, it can be seen that among the modified accelerators, when rosin glyceride is not added or rosin glyceride is replaced with an equal amount of rosin, the time at which the blooming phenomenon occurs in the accelerator dispersion master batch is significantly shortened, and the stability of the accelerator dispersion master batch is significantly reduced.

[0198] In combination with Example 2 and Examples 4-9 and in combination with the data in Table 1, it can be seen that among the carriers, when the weight ratio of oil-extended EPDM, non-oil-extended EPDM, ethylene-vinyl acetate copolymer, and rosin is in the range of (30-40):(60-70):(30-40):(10-20), the stability of the accelerator dispersion master batch can be effectively improved, and the accelerator dispersion master batch still has a relatively low powder content after long-term storage.

[0199] In combination with Example 10 and Example 12 and in combination with the data in Table 1, it can be seen that when the ethylene-vinyl acetate copolymer is maleic anhydride grafted ethylene-vinyl acetate copolymer, the growth rate of the powder content of the accelerator dispersion master batch can be further effectively reduced, and the accelerator dispersion master batch has no blooming phenomenon on the surface after long-term storage, and the stability of the accelerator dispersion master batch is effectively improved.

[0200] This specific embodiment is merely an explanation of the present application and is not a limitation on the present application. Those skilled in the art can make modifications to this specific embodiment without creative contribution after reading this specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the Patent Law.

Claims

1. A promoter dispersion masterbatch characterized by: The raw materials include the following components by weight: carrier 25-40 parts, modified accelerator 60-75 parts; the carrier includes oil-extended ethylene-propylene-diene rubber, non-oil-extended ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and rosin, and the weight ratio of the oil-extended ethylene-propylene-diene rubber, non-oil-extended ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and rosin is (20-60):(40-80):(10-40):(10-40); the modified accelerator includes accelerator and rosin glyceride, and the weight ratio of the accelerator and rosin glyceride is (70-80):(20-30); the accelerator is zinc dimethyl dithiocarbamate.

2. The accelerator dispersant masterbatch according to claim 1, characterized in that: The weight ratio of the oil-extended ethylene-propylene-diene rubber, non-oil-extended ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and rosin is (30-40):(60-70):(30-40):(10-20).

3. The accelerator dispersant masterbatch of claim 1, wherein: The weight ratio of the oil-extended ethylene-propylene-diene rubber, non-oil-extended ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and rosin is 35:65:35:

15.

4. The accelerator dispersant masterbatch of claim 1, wherein: The oil-extended ethylene-propylene-diene rubber includes non-oil-extended ethylene-propylene-diene rubber and filling oil, and the weight ratio of the non-oil-extended ethylene-propylene-diene rubber and filling oil is (60-70):(30-40).

5. The accelerator dispersant masterbatch according to any one of claims 1 to 4, characterized in that: The melt index of the ethylene-vinyl acetate copolymer is 3-4 g / 10 min.

6. The accelerator dispersant masterbatch according to any one of claims 1 to 4, characterized in that: The ethylene-vinyl acetate copolymer is maleic anhydride grafted ethylene-vinyl acetate copolymer.

7. A process for the preparation of accelerator dispersion masterbatch as claimed in any one of claims 1 to 6, characterized in that: The method includes the following steps: The oil-extended ethylene-propylene-diene rubber, non-oil-extended ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and rosin are uniformly mixed in a proportion to obtain a carrier; the accelerator and rosin glyceride are uniformly mixed in a proportion, and then melted and extruded at 70-110 ℃, and then granulated to obtain a modified accelerator; the carrier and the modified accelerator are uniformly mixed to obtain a premix; the premix is melted and extruded at 170-200 ℃, and then granulated to obtain a promoter dispersion master batch.

8. The method of claim 7, wherein the accelerator dispersion masterbatch is prepared by: The melting and extrusion of the modified accelerator is performed in a twin-screw extruder, and the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 75-80 ℃, the temperature of the melting section is 80-85 ℃, the temperature of the plasticizing section is 80-85 ℃, and the temperature of the discharging section is 85-90 ℃.

9. The method of claim 7, wherein the accelerator dispersion masterbatch is prepared by: The melting and extrusion of the promoter dispersion master batch is performed in a twin-screw extruder, and the screw of the twin-screw extruder is sequentially divided into a conveying section, a melting section, a plasticizing section and a discharging section along the conveying direction of the material, the temperature of the conveying section is 180-185 ℃, the temperature of the melting section is 185-190 ℃, the temperature of the plasticizing section is 190-195 ℃, and the temperature of the discharging section is 195-200 ℃.

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