CN104987724A - Silicone master batch with high silicone content and preparation method of silicone master batch - Google Patents

Abstract

The invention relates to a silicone masterbatch with high silicone content and a preparation method thereof, belonging to the technical field of polymer materials. The silicone masterbatch with high silicone content is made of the following raw materials in the following weight proportions, mixed by a mixer, extruded and granulated by a twin-screw extruder, and its silicone content can be higher than 50%: silicone 50-65 %, carrier resin 5-40%, compatibilizer 5-30%, filler 0-10%, additive 0-5%. Adding the silicone masterbatch with high silicone content of the present invention can keep the basic mechanical properties of the material well, and further effectively improve the friction resistance and processing performance of the material, greatly improve the production efficiency, and satisfy the It meets the requirements of the automobile, electronic appliances and other industries on the processing performance and friction resistance of materials.

Description

A kind of silicone masterbatch with high silicone content and preparation method thereof

technical field

The invention relates to the technical field of polymer materials, in particular to a silicone masterbatch with high silicone content and a preparation method thereof.

Background technique

Polyorganosiloxane is a kind of polymer with repeated Si-O bonds as the main chain. Since a series of organic substituents can be connected to the silicon atom position, polysiloxane is a kind of polymer between organic and inorganic. Special polymer materials, with many unique physical properties, can be used as cost-effective processing aids and modifiers in the production of thermoplastics. (Yilgor E, et al. Progress in Polymer Science 2014;39(6):1165-1195) Silicone masterbatch is mainly composed of ultra-high molecular weight polysiloxane (hereinafter referred to as "silicone") and carrier resin (general-purpose Plastic) is a functional additive combined.

Compared with traditional processing aids, silicone masterbatches have higher stability, better lubricity and slip (Yilgor I, et al. Polymer 2011;52(2):266–274.) . In terms of improving the processability of plastics, silicone masterbatch can reduce the melt viscosity and improve the processability and fluidity of thermoplastic blends, increase the melting rate and deformability of plastics, and improve the mold filling and mold release properties of materials, effectively Prevent melt fracture, reduce the occurrence of problems such as screw slippage, warping, and weld marks during processing, and reduce the defective rate of products. Silicone masterbatches can also reduce processing energy by reducing extruder torque and die pressure. (Yilgor I, et al. J Appl Polym Sci 2002;83(8):1625–1634.) During the blending modification process, when more mineral fillers are contained, the silicone masterbatch can reduce die salivation and mold deposits production, which improves production efficiency. In terms of improving the surface properties of products, the addition of silicone masterbatch can significantly reduce the friction coefficient of materials, improve surface gloss, enhance surface touch, improve friction resistance, scratch resistance, weather resistance, corrosion resistance and aging resistance. Beautify the appearance effect and improve the expressive force of the product. In addition, the impact strength and elongation of the product can be improved without changing the physical properties of the plastic. Good non-migration, does not affect the subsequent processing of the product (such as spraying, printing, electroplating), and has better cost-effectiveness. Silicone masterbatches have been widely used in the fields of cables and cables, automotive interiors, plastic heat insulation seals, thin-walled special-shaped complex plastic parts, shells and drive components of commercial machines, high-end footwear and other fields.

Faced with such a broad market, some foreign companies represented by Dow Corning and Degussa have been in a monopoly position for a long time, and their efficient production technology and high silicone content have been beyond the reach of domestic companies. Silicone masterbatches with high silicone content can reduce the dosage while improving product quality without changing the cost, but the compatibility and dispersion between silicone and carrier resin have always been technical difficulties that hinder the increase of silicone content.

Chinese patent CN 1687237A discloses a preparation method of organosilicone micropowder. The method prepares organosilicon copper micropowder through steps such as preparation of dispersion liquid, dispersion and crosslinking of active silicone oil, and aging of crosslinked organosilicon particles. Although silicone powders with different particle sizes can be prepared by controlling the amount of dispersant and shear stirring speed, it is difficult to fundamentally solve the compatibility and dispersion between silicone and carrier resin, and the preparation process is complicated.

China Patent CN 103524822A discloses a foamed silicone masterbatch and its preparation method and application. The foamed silicone masterbatch is made by blending thermoplastic polymer resin, silicone powder, foaming agent and antioxidant. Although the use of foaming technology reduces the density of the masterbatch, the number of silicone masterbatches per unit mass is significantly increased, thereby improving the dispersion of the silicone masterbatch in the matrix resin, but the silicone content in the masterbatch has not yet been obtained. Further improve.

For this reason, how to ensure good compatibility and dispersion between silicone and carrier resin while increasing the silicone content is a subject to be further studied.

Contents of the invention

The purpose of the present invention is to provide a silicone masterbatch with high silicone content and its preparation method for the defects of low silicone content and complicated preparation process of the existing silicone masterbatch. Compared, the silicone masterbatch with a silicone content of more than 50% can be obtained by mixing and extruding granulation, which can effectively improve the processing performance and friction resistance of the material while maintaining the basic mechanical properties of the material.

The purpose of the present invention can be achieved through the following technical solutions.

A silicone masterbatch with high silicone content is characterized in that it is made of the following raw materials in weight ratio:

Silicone 50-65%

Carrier resin 5-40%

Compatibilizer 5-30%

Filler 0-10%

Auxiliary 0-5%

The silicone is selected from high molecular weight silicone oils with a number average molecular weight greater than 400,000 of the following structure:

Among them, R is an alkyl or aryl group; X is an alkyl, aryl, alkenyl, hydroxyl or alkoxy group, etc.; R' is an alkyl, aryl, hydrogen or carbon functional group, etc.; n, m=0, 1, 2, 3..., but not 0 at the same time;

The silicone can also be selected from one or more of the following silicone rubbers: dimethyl silicone rubber (MQ), namely methyl silicone rubber, methyl vinyl silicone rubber (VMQ) or methyl phenyl vinyl Silicone rubber (PVMQ).

The silicone can also be formed by combining the above-mentioned high molecular weight silicone oil and silicone rubber.

The carrier resin is selected from thermoplastic polyolefin resins, such thermoplastic polyolefin resins are obtained by homopolymerization or copolymerization of ethylene, propylene, styrene, vinyl acetate, butadiene, and ɑ-methylstyrene monomers, such as polypropylene (PP), polyethylene (PE), polystyrene (PS), ethylene-vinyl acetate copolymer (EVA), etc. and their combinations.

The compatibilizer is a polar monomer graft polymer, wherein the polymer matrix can be selected from two or more monomer copolymers in styrene, butadiene, ethylene and propylene, and can also include The mixture of these copolymerization products may also include oxides of copolymerization products or their mixtures, such as styrene-butadiene block copolymer (SBS), hydrogenated styrene-butadiene block copolymer (SEBS), etc.; Polar monomers may be selected from maleic anhydride, acrylic acid and their derivatives, and blends thereof may also be included.

The fillers include silicate fillers, such as talcum powder, kaolin, molecular sieve, etc., and may also be calcium carbonate fillers, or a mixture of silicate fillers and calcium carbonate fillers.

The auxiliary agent is a processing aid, including an ultraviolet light stabilizer, a thermal oxygen stabilizer or a combination thereof.

Described ultraviolet stabilizer is ultraviolet absorber UV-P.

The thermal oxygen stabilizer is antioxidant B245 or antioxidant AT10.

The preparation method of the silicone master batch with high silicone content is carried out according to the following process steps:

Step 1: Weigh the carrier resin, compatibilizer, filler and auxiliary agent respectively according to the weight ratio of raw materials;

Step 2: Place the raw materials weighed in step 1 in a mixer with a rotating speed of 400-1000 rpm and mix for 5 minutes;

Step 3: Extrude and granulate the mixed material in step 2 together with the silicone weighed according to the weight ratio through a twin-screw extruder at 120-240°C and 200-300 rpm to obtain a silicone masterbatch.

The beneficial technical effects of the present invention are:

1. The present invention realizes the preparation of a silicone masterbatch with a silicone content higher than 50% by selecting a compatibilizer with a specific structural design and mass ratio for different matrix resins and silicone to mix, extrude and granulate.

2. The present invention can further ensure the stability of the silicone masterbatch during processing by adding additives.

3. The silicone masterbatch prepared by the present invention is a recyclable material, and the raw materials for preparation do not contain plasticizers that damage the environment. The production efficiency is high, the process is simple and environmentally friendly.

4. In the entire processing method of the present invention, each process step is integrated and interrelated. Through the step-by-step implementation of each process step, the formula system is well blended, extruded and granulated, and the prepared high silicone content Silicone masterbatch can better maintain the basic mechanical properties of the material and further effectively improve the friction resistance and processing performance of the material, which satisfies the requirements of the automobile, electronic appliances and other industries on the friction resistance of materials.

Detailed ways

Example 1

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 50%

Carrier resin 39.5%

Compatibilizer 10%

Auxiliary 0.5%

The silicone is methyl silicone oil with a number average molecular weight of 1 million;

The carrier resin is low-density polyethylene (LDPE), 2426K;

The compatibilizer is hydrogenated styrene-butadiene block copolymer (SEBS), Baling Petrochemical YH 501;

The auxiliary agent is antioxidant B245.

First weigh the carrier resin, compatibilizer, and additives and mix them in a mixer with a rotation speed of 400-600rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through a twin-screw extruder at 120 Extrude and granulate at -160°C with a rotation speed of 200-300 rpm to obtain a silicone masterbatch.

Example 2

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 65%

Carrier Resin 19.2%

Compatibilizer 15%

Auxiliary 0.8%

The silicone is a methyl vinyl silicone rubber with a molecular weight of 700,000;

The carrier resin is homopolypropylene (PP), T30S;

The compatibilizer is styrene-butadiene block copolymer (SBS), Baling Petrochemical YH-791;

Described auxiliary agent is antioxidant B245 and ultraviolet absorber UV-P;

First weigh the carrier resin, compatibilizer and additives and mix them in a mixer with a rotation speed of 600-800rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through the twin-screw extruder at 190 Extrude and granulate at -240°C with a rotational speed of 200-300 rpm to obtain a silicone masterbatch.

Example 3

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 55%

Carrier resin 29.7%

Compatibilizer 15%

Auxiliary 0.3%

Described silicone is the methyl silicone oil that molecular weight is 750,000;

The carrier resin is homopolymerized high-impact polystyrene (HIPS), Taiwan Chimei PH88;

Described auxiliary agent is antioxidant AT10 and ultraviolet absorber UV-P;

The compatibilizer is styrene-butadiene block copolymer (SBS), Baling Petrochemical YH-802.         

First weigh the carrier resin, compatibilizer and additives and mix them in a mixer with a rotation speed of 800-1000rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through a twin-screw extruder at 200 Extrude and granulate at -240°C with a rotational speed of 200-300 rpm to obtain a silicone masterbatch.

Example 4

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 60%

Carrier resin 10%

Compatibilizer 29.4%

Filler 0.5

Auxiliary 0.1%

The silicone is composed of methyl vinyl silicone rubber (VMQ) with a molecular weight of 700,000 and 30% of 800,000 methyl silicone oil, each accounting for 30% of the total weight of raw materials;

The carrier resin is ethylene-vinyl acetate copolymer (EVA), Formosa Plastics 7340M;

The filler is talcum powder, 3000 mesh;

The compatibilizer is styrene-butadiene block copolymer (SBS), Baling Petrochemical YH-802.

First weigh the carrier resin, compatibilizer, filler and additives and mix them in a mixer with a rotation speed of 400-1000rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through the twin-screw extruder Extrude and granulate at 160-200°C with a rotation speed of 200-300 rpm to obtain a silicone masterbatch.

Example 5

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 50%

Carrier resin 30%

Compatibilizer 20% 20%

The silicone is composed of dimethyl silicone rubber (MQ) with a molecular weight of 700,000 and 15% of methylphenylvinyl silicone rubber (PVMQ) with a molecular weight of 600,000, each accounting for 35% of the total weight of raw materials;

The carrier resin is composed of 15% polypropylene PP (T30S) and 15% low density polyethylene LDPE (2426K) each accounting for the total weight of raw materials;

The compatibilizer is hydrogenated styrene-butadiene block copolymer (SEBS), Baling Petrochemical YH 501.

First weigh the carrier resin and compatibilizer and mix them in a mixer with a speed of 500-800rpm for 5 minutes; then pass the mixed material together with the weighed silicone through a twin-screw extruder at 190-240°C , the rotation speed is 200-300 rpm to obtain the silicone masterbatch by extruding and granulating.

Example 6

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 55%

Carrier resin 15%

Compatibilizer 20%

Filler 5%

Auxiliary 5%

The silicone is composed of methyl vinyl silicone rubber (VMQ) with a molecular weight of 700,000 and 5% of methyl silicone oil with a molecular weight of 1 million, each accounting for 50% of the total weight of raw materials;

The carrier resin is polypropylene (PP), T30S;

The compatibilizer is styrene-butadiene block copolymer (SBS), Baling Petrochemical YH-791;

The filler is talcum powder, 3000 mesh;

Described auxiliary agent is antioxidant B245 and ultraviolet absorber UV-P;

First weigh the carrier resin, compatibilizer, additives and fillers and mix them in a mixer with a rotation speed of 600-800rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through the twin-screw extruder Extrude and granulate at 190-240°C with a rotation speed of 200-300 rpm to obtain a silicone masterbatch.

Example 7

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 53%

Carrier resin 20%

Compatibilizer 17%

Filler 10%

The silicone is methyl vinyl silicone rubber (VMQ) with a molecular weight of 700,000;

The carrier resin is polypropylene (PP), T30S;

The compatibilizer is styrene-butadiene block copolymer (SBS), Baling Petrochemical YH-791;

The filler is talcum powder, 3000 mesh.

First weigh the carrier resin, compatibilizer and filler and mix them in a mixer with a rotation speed of 600-800rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through the twin-screw extruder at 190- Extrude and granulate at 240°C with a rotational speed of 200-300 rpm to obtain a silicone masterbatch.

Comparative example 1

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 0%

Carrier resin (PP) 84.2%

Compatibilizer 15%

Auxiliary 0.8%

The carrier resin is polypropylene (PP), T30S;

Described auxiliary agent is antioxidant B245 and ultraviolet absorber UV-P;

The compatibilizer is styrene-butadiene block copolymer (SBS), Baling Petrochemical YH-791.       

First weigh the carrier resin, compatibilizer, and additives and mix them in a mixer with a rotation speed of 400-1000rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through a twin-screw extruder at 190 Extrude and granulate at -240°C with a rotational speed of 200-300 rpm to obtain a silicone masterbatch.

Comparative example 2

A silicone masterbatch with high silicone content, the weight ratio of raw materials is as follows:

Silicone 40%

Carrier resin (PP) 44.2%

Compatibilizer 15%

Auxiliary 0.8%

The silicone is methyl vinyl silicone rubber (VMQ) with a molecular weight of 500,000;

The carrier resin is polypropylene (PP), T30S;

Described auxiliary agent is antioxidant B245 and ultraviolet absorber UV-P;

The compatibilizer is styrene-butadiene block copolymer (SBS), Baling Petrochemical YH-791.       

First weigh the carrier resin, compatibilizer, and additives and mix them in a mixer with a rotation speed of 400-1000rpm for 5 minutes; then pass the mixed materials together with the weighed silicone through a twin-screw extruder at 190 Extrude and granulate at -240°C with a rotational speed of 200-300 rpm to obtain a silicone masterbatch.

Dry the masterbatches prepared in Examples 1-7 and Comparative Examples 1-2 in a blast oven at 80-100°C for 2-3 hours, and then add 3% by weight masterbatches to the block copolymerization Melt blending in PP resin to prepare molding samples. Among them, the tensile performance test and bending performance test are carried out according to GB/T 1040.2-2006 and GB/T 9341-2008 respectively; the friction performance is carried out according to GB/T 3960-1983, the set load is 200N, and the sliding line speed is 200r/ min, the friction time is 1h.

After testing, the relevant test data of Examples 1-7 and Comparative Examples 1-2 added to PP resin as masterbatches to prepare products are shown in Table 1 below:

It can be seen from the comparison of the performance data obtained by the products of Examples 1-7 and Comparative Examples 1-2 that compared with polypropylene resin without adding silicone masterbatch and adding the same percentage of low silicone content silicone masterbatch The increase of the silicone content in the silicone masterbatch can effectively improve the friction resistance and processing performance of the material, and at the same time, the basic mechanical properties of the material can also be well maintained. In summary, the addition of silicone masterbatches with high silicone content can well meet the requirements of the automobile, electronic appliances and other industries for material processing performance and friction resistance.

The above examples are only for illustrating the present invention, and are not intended to limit the present invention. Those skilled in the relevant art can make corresponding adjustments and changes without departing from the scope of the present invention. Therefore, all equivalent technical solutions belong to the category of the present invention, and the scope of patent protection of the present invention is defined by each claim.

Claims (10)

1. a silicone masterbatch for high silicone content, is characterized in that being made up of the raw material of following weight proportion:

Silicone 50-65%

Vector resin 5-40%

Compatilizer 5-30%

Filler 0-10%

Auxiliary agent 0-5%.

2. the silicone masterbatch of high silicone content according to claim 1, is characterized in that: the high molecular silicone oil that the number-average molecular weight that described silicone is selected from following structure is greater than 400,000:

Wherein, R is alkyl or aryl; X is alkyl, aryl, thiazolinyl, hydroxyl or alkoxyl group; R ' is alkyl, aryl, hydrogen or carbon functional group; N, m=0,1,2,3 ..., but be asynchronously 0.

3. the silicone masterbatch of high silicone content according to claim 1, is characterized in that: described silicone is selected from one or more in following silicon rubber: dimethyl silicone rubber, methyl vinyl silicone rubber or methyl phenyl vinyl silicone rubber.

4. the silicone masterbatch of the high silicone content according to claim 1,2 or 3, is characterized in that: described silicone is formed by high molecular silicone oil and rubber composition.

5. the silicone masterbatch of high silicone content according to claim 1, is characterized in that: described vector resin is selected from polypropylene, polyethylene, polystyrene or ethylene-vinyl acetate copolymer, or their combination.

6. the silicone masterbatch of high silicone content according to claim 1, it is characterized in that: described compatilizer is polar monomer graft polymkeric substance, wherein: polymeric matrix is selected from two or more the monomer copolymer in vinylbenzene, divinyl, ethene, propylene, or be the mixture comprising these copolymerization products, also or be the oxide compound or their mixture that comprise copolymerization product, as styrene-butadiene block copolymer SBS, hydrogenated styrene-butadiene block copolymer SEBS; Polar monomer is selected from maleic anhydride, vinylformic acid and derivative thereof, also can comprise their blend.

7. the silicone masterbatch of high silicone content according to claim 1, is characterized in that: described filler is selected from silicate filler or pearl filler, or their combination.

8. the silicone masterbatch of the high silicone content according to claim 1 or 7, is characterized in that: described silicate filler is selected from talcum powder, kaolin or molecular sieve.

9. the silicone masterbatch of high silicone content according to claim 1, is characterized in that: described auxiliary agent is processing aid, comprises UV light stabilizing agent, thermal oxidation stabilizer or its combination.

10. the preparation method of the silicone masterbatch of high silicone content according to claim 1, is characterized in that: processing step is as follows:

Step 1: take vector resin, compatilizer, filler and auxiliary agent respectively by the weight proportion of raw material;

Step 2: the blender that raw material step 1 taken is placed in rotating speed 400-1000 rpm mixes 5 minutes;

Step 3: the material that step 2 is mixed together with the silicone taken by weight ratio together by twin screw extruder at 120-240 DEG C, rotating speed is that under 200-300 rpm, extruding pelletization obtains silicone masterbatch.