Trans-1,4-butadiene-isoprene copolymer composite rubber filled with nanometer silica and preparation method thereof

A nano-silica and isoprene technology, applied in the field of synthetic rubber, can solve the problems of difficult in-situ addition of fillers, reduced molecular weight and polymerization yield of polymerized products, and no fundamental solution to in-situ polymerization. The effect of improving flexural fatigue and improving resilience

Active Publication Date: 2019-05-03
SHANDONG HUAJU POLYMER MATERIALS CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] For coordination polymerization, since its catalyst system is very sensitive to water, oxygen, etc., it usually requires anhydrous and oxygen-free polymerization conditions, so it is difficult to achieve in-situ addition of fillers.
There are bibliographical reports on the preparation of PP / nanometer calcium carbonate in-situ composite nanomaterials, but the addition concentration of its filler is very low. Once the concentration of calcium carbonate becomes high, the polymerization rate of propylene obviously declines, and the molecular weight and polymerization yield of the polymerization product obviously reduce ( Synthetic Resins and Plastics, 2003; China Plastics, 2003)
Therefore, although there are reports in the literature on the in-situ preparation of rubber / silica filler composites (Guangdong Chemical Industry, 2015; CN101418063 B), it is essentially the co-precipitation of silica or modified silica and rubber emulsion. method preparation, did not fundamentally solve the problem of in-situ polymerization of nano fillers such as silica in the process of coordination polymerization of olefin or diene monomer

Method used

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  • Trans-1,4-butadiene-isoprene copolymer composite rubber filled with nanometer silica and preparation method thereof
  • Trans-1,4-butadiene-isoprene copolymer composite rubber filled with nanometer silica and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0040] Add 150 grams of silicon dioxide (30nm) that has been roasted in vacuum at 700°C for 6 hours, 1500 mL of isoprene monomer, and 100 mL of butadiene in sequence into the high-speed mixer at a stirring speed of 1500 r / min for 5 minutes, then add 15 mmol tri Isobutyl aluminum, stirring speed 2000r / min, stirred for 5 minutes, then added 0.43g of heterogeneous Ziegler-Natta catalyst (wherein, the titanium compound is selected from TiCl 4 The mass content of titanium is 2.0%, and the inner electron donor ethyl benzoate mass content is 6%), and above-mentioned material is transported in the polymerizer of 3L, and copolymerization reaction temperature is 10 ℃, and the mol ratio of hydrogen and two monomers is 0.01:100, the copolymerization time is 71 hours. The material is transported to the extruder, and 200ml of ethanol and 10 grams of antioxidant 264 are added to the extruder at the same time to terminate the polymerization, remove unreacted monomers, extrude and granulate, a...

Embodiment 2

[0042] The operation is the same as in Example 1, except adding silicon dioxide, isoprene and butadiene to the high-speed mixer to process the monomers, and also adding 30 g of environmentally friendly aromatic oil and hydrogen, wherein the molar ratio of hydrogen to the two monomers is 0.001:100. The results are shown in Table 1.

Embodiment 3

[0044] Add 5 grams of nano-silica (30nm), 1500mL of isoprene monomer, and 250ml of butadiene into the high-speed mixer in sequence, and stir at a speed of 2000r / min for 5 minutes, and then add 25mmol of three The diphenyldimethoxysilane of isobutyl aluminum and 10mmol, stirring speed 2000r / min, stir 5 minutes, then add the heterogeneous phase Ziegler-Natta catalyst of 1.2g (wherein, titanium compound is selected from TiCl 4 The mass content of titanium is 4%), in the horizontal self-cleaning reactor of above-mentioned material delivery 5L, copolymerization reaction temperature is 10 ℃, and the mol ratio of hydrogen and two monomers is 0.08:100, and copolymerization time is 9 hours. The material is transported to the extruder, and 200ml of water and 5 grams of anti-aging agent 264 are added to the extruder at the same time to terminate the polymerization, remove unreacted monomers, extrude and granulate, and obtain trans-1,4-butadiene-iso 325 grams of pentadiene copolymerized c...

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Abstract

Provided is nano-silicon dioxide filled trans-1,4-butadiene-isoprene copolymer composite rubber. A preparation method comprises the steps that nano-silicon dioxide obtained after vacuum drying or high-temperature calcination is dispersed in an isoprene-butadiene mixed monomer in advance, alkylaluminum and external electron donor are added in sequence, high-speed stirring and mixing are conducted to be uniform, a supported Ziegler-Natta catalyst is added, the mixture is added into a polymerization kettle, and isoprene-butadiene is catalyzed to be synthesized to be butadiene-isoprene copolymer composite rubber with the trans-1,4-structure content larger than 85 mol% in a copolymerization mode, wherein in the composite rubber, the trans-1,4-butadiene-isoprene copolymer mass content is 50-99.9%, and the nano-silicon dioxide mass content is 0.1-50%; a copolymer is composed of an isoprene monomer unit with the mole fraction being 50-98% and a butadiene monomer unit with the mole fraction being 2-50%. For the trans-copolymer composite rubber, due to the fact that nano-silicon dioxide is uniformly dispersed at the nanoscale, abrasion resistance and wet-skid resistance of products can be significantly improved, and meanwhile the crack resistance initiation performance of the products is greatly improved, and the nano-silicon dioxide filled trans-1,4-butadiene-isoprene copolymer composite rubber is suitable for high-performance rubber products and light-color rubber products.

Description

technical field [0001] The invention belongs to the field of synthetic rubber, in particular to nano-silica-filled trans-butylene copolymer composite rubber and an in-situ polymerization preparation method thereof. Background technique [0002] In order to improve key properties such as strength and wear resistance of rubber products, it is necessary to add a large amount of fillers such as carbon black and silica. There are usually two methods of adding fillers to rubber, dry and wet. The traditional addition method is to physically and mechanically blend rubber and fillers. Although the physical blending method is simple, the mixing effect is poor, the power consumption is large, and carbon black, white carbon black, etc. are flying to pollute the environment, and the dispersion effect of fillers in rubber Not ideal, it is easy to partially form large-sized aggregates, which will affect fatigue performance, heat generation, wear resistance, etc. [0003] Compared with dr...

Claims

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Application Information

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Patent Type & AuthorityPatents(China)
IPC IPC(8): C08L9/00C08K3/36C08F236/08C08F236/06C08F2/44C08F4/02C08F4/642C08F4/649C08F4/68
CPCC08F236/08C08K3/36C08L9/00C08F236/06C08F2/44C08F4/02C08F4/6421C08F4/6494C08F4/68
Inventor王日国贺爱华邵华锋
OwnerSHANDONG HUAJU POLYMER MATERIALS CO LTD