A kind of polyisocyanate prepolymer coupling agent and preparation method thereof

A polyisocyanate and polyisocyanate technology, applied in the field of polyisocyanate prepolymer coupling agent and its preparation, can solve the problem that white carbon black cannot be effectively melted into the rubber compound, the rubber compound cannot be cured and formed, and the elastic memory cannot be Advanced problems, to achieve the effect of improving stiffness, good mixing and forming, and enhancing compatibility

CN104098788BActive Publication Date: 2017-02-08CHINA PETROLEUM & CHEM CORP
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Publication Date
2017-02-08

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Abstract

The invention discloses a polyisocyanate-prepolymer coupling agent and a preparation method thereof. The coupling agent comprises the following composition in parts by mass: a diisocyanate, and polyisocyanate prepolymers respectively with the average functionality of 3, 4, 5, 6, 7 and 8. The preparation method of the coupling agent comprises: mixing a trimethanol compound with diisocyanate according to a molar ratio of 1:2.98-3.02, and reacting at 75-80 DEG C, so as to obtain the polyisocyanate prepolymer with the average functionality of 3; repeating the above step by changing the molar ratio of the trimethanol compound to diisocyanate into 1:2.48-2.52, 1:2.31-2.35, 1:2.23-2.27, 1:2.18-2.22 and 1:2.15-2.19, so as to respectively prepare the polyisocyanate prepolymers respectively with the average functionality of 4, 5, 6, 7 and 8; and then mixing the prepared polyisocyanate prepolymers respectively with the average functionality of 3, 4, 5, 6, 7 and 8 with the diisocyanate according to a ratio, so as to obtain the coupling agent. The coupling agent is high in coupling efficiency, and a coupled butadiene-styrene polymer possesses amido groups with multiple polarities and has high and wide-distribution molecular weight. The preparation method is simple and rapid, and industrialized production can be realized.
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Description

technical field

[0001] The invention discloses a polyisocyanate prepolymer coupling agent and a preparation method thereof, belonging to the field of modification of styrene-butadiene rubber. Background technique

[0002] Styrene and conjugated diene can be directionally polymerized into a random copolymer under the trigger of butyllithium in a solvent. This material is especially suitable for making tires. As an ultra-high performance tire compound, SSBR with high vinyl content, high cis-butadiene rubber and white carbon black are its main components. However, due to the low Weissenbery effect and elastic memory effect of general-purpose SSBR, during the mixing process of high-cis-rare-earth polybutadiene rubber and white carbon black with high molecular chain regularity and high cold flow in the internal mixer, the rubber The shear force of the material in the mixing process is insufficient, the frictional heat generation is low, the rotor of the internal mixer seems to b...

Examples

Embodiment 1

[0067] (1) In a clean and dry 1000mL three-necked bottle under the protection of nitrogen, add anhydrous 425mL toluene, TMP80g, TDI290.58g respectively, at this time TMP / TDI=1:3.02 (mass ratio), in After stirring at a constant temperature of 75-80°C for 6-8 hours, the measured solid content was 49.6wt%, and the concentration of isocyanate was 0.83mol / L. The average functionality of the adduct molecule contains 3 -NCO.

[0068] (2) Add anhydrous 425mL toluene, TMP80g and TDI239.60g respectively in a clean and dry 1000mL three-necked bottle under the protection of nitrogen gas. At this time, TMP / TDI=1:2.52 (mass ratio), constant temperature After stirring for 6-8 hours at 75-80°C, the measured solid content was 50.3wt%, and the concentration of isocyanate was 0.74mol / L. The average functionality of the adduct molecule contains 4 -NCO.

[0069] (3) Add anhydrous 425mL toluene, TMP80g and TDI219.87g respectively in a clean and dry 1000mL three-necked bottle under the protection ...

Embodiment 2

[0075] Steps (1) to (6) are the same as in Example 1,

[0076] Take 2mL of chemically pure TDI with a mass content of 99%, 15mL of the prepolymer in (1), 20mL of the prepolymer in (2), 35mL of the prepolymer in (3), 15mL of the prepolymer in (4), Inject 18mL of the prepolymer in (5) and 3mL of the prepolymer in (6) into a 100mL dried volumetric flask, then add an appropriate amount of toluene and mix well to make a polyisocyanate with an isocyanate concentration of 0.85mol / L. Isoacid coupling agent.

Embodiment 3

[0078] Under the protection of nitrogen, add 3.5 L of hexane-cyclohexane mixed solvent and 0.98 g of tetrahydrofurfuryl alcohol ethyl ether into a 5-liter polymerization kettle, start stirring within 40 minutes, and continuously and uniformly add 0.5 mol / L of n-butyl Lithium 13mL, and 132.5g of styrene and 397.5g of butadiene mixed monomers, the polymerization is carried out at 50-75°C, after the addition of the monomers, react for 25min, and then add the isocyanate concentration in Example 1. 9.5mL of 0.68mol / L prepolymer was subjected to coupling reaction, the coupling reaction temperature was 60-75°C, and the time was 25min. The obtained one-arm to eight-arm SSBR was filled with 198.1g of TDAE oil, condensed and dried to obtain SSBR filled Oil raw rubber, in which the number average molecular weight of single-arm polymer is 8.1×10 4 , the average number average molecular weight of the conjugate is 42×10 4 , molecular weight distribution index 2.23, vinyl content 74.6%, Moo...