CN100448902C - High melt strength polypropylene resin and preparation method thereof - Google Patents

Abstract

The invention relates to a high melt strength polypropylene resin and a preparation method thereof. High melt strength polypropylene resin is composed of component A, component B and component C: the weight percentage of component A is 70% to 99.8%, the weight percentage of component B is 0.1% to 29.9%, and the weight percentage of component C is The weight percentage of component B is 0.1% to 25%; the optimal range of weight percentage of component B is 0.1% to 20%, and the optimal range of weight percentage of component C is 0.1% to 10%. Among them, component A is original ecological polypropylene resin, component B is vinyl polybutadiene, and component C is acrylic ester compound. The preparation method is as follows: after mixing the above components evenly, put them into the material cavity from the feeding port of the melting and grafting reaction equipment, and carry out the melting and grafting reaction. The reaction temperature is 190-240 ° C. After the reaction, high melt Strength polypropylene resin. The obtained product has high melt strength, no decline in basic mechanical properties, and good application effect.

Description

High melt strength polypropylene resin and preparation method thereof

technical field

The invention relates to a high melt strength polypropylene resin and a preparation method thereof

Background technique

Polypropylene is a widely used general-purpose plastic. It has many excellent properties, such as low relative density, tasteless and odorless, edible oil resistance, excellent corrosion resistance, good electrical properties and chemical stability, and low price and large output. , second only to PVC and PE. However, polypropylene has poor toughness, low temperature brittleness, and low thermal deformation temperature; and the chain structure of polypropylene is linear, and polypropylene has no strain hardening effect in the molten state, resulting in low melt strength and poor sag resistance. Disadvantages, thus greatly limiting the application of polypropylene. At the same time, the softening point of polypropylene is close to the melting point. When the temperature is higher than the melting point, its melt strength and melt viscosity drop sharply, resulting in uneven wall thickness of the product during thermoforming, and edges appear during extrusion, coating, and calendering. Curl shrinkage, cell collapse during extrusion and foaming, etc. Therefore, it is imperative to develop polypropylene with strain hardening effect in molten state, that is, high melt strength polypropylene.

At present, the methods for preparing high melt strength polypropylene are mainly divided into two categories: one is the reaction modification of polypropylene and other compounds; the other is the blending modification of polypropylene and other polymers. The specific implementation methods mainly include: ray irradiation method, reaction extrusion method, post-polymerization kettle method, solution grafting method, dynamic cross-linking method, melt blending modification method, etc.

Patents CN1045107A and CN1055372A describe the use of peroxides to initiate grafting modification of polypropylene powder in a polymerization tank to obtain strain-hardened polypropylene resin. Another patent (CN1432596A) adopts 2,5 dimethyl-2,5 double 8 tert-butylperoxyhexane and diacrylate-1,6-butanediol acetone solution mixed by injection into the twin-screw extruder In the melt of polypropylene powder, grafting is carried out to obtain polypropylene resin with high melt strength. A public report (Journal of Applied Polymer Science, vol.61, 1395-1404, 1996) uses polypropylene and multifunctional monomer pentaerythritol triacrylate to react in the presence of peroxides to prepare high melt strength polypropylene. Another report (Journal of Applied Polymer Science, vol.66, 809-819, 1997) used polypropylene, polyethylene, and trimethyltriacrylate under the action of peroxide to prepare branched High melt strength polypropylene. In addition, under the action of peroxides, acrylate monomers can be melt-grafted with polypropylene to prepare highly branched polypropylene resins ("China Plastics", Volume 16, Issue 10, 24-28, 2002). It can be seen from the above reports that peroxides are used as initiators in the preparation of high melt strength polypropylene. However, the introduction of peroxides can degrade polypropylene to a great extent and greatly reduce the mechanical properties of polypropylene. In addition, it will increase the cost of high melt strength polypropylene resin products and reduce the competitive position of products in the market.

Contents of the invention

The object of the present invention is to provide a high melt strength polypropylene resin.

Another object of the present invention is to provide a method for the preparation of high melt strength polypropylene resin.

Technical embodiment of the present invention is as follows:

High melt strength polypropylene resin, which is composed of component A, component B and component C: the weight percentage of component A is 70% to 99.8%, and the weight percentage of component B is 0.1% to 29.9% , the weight percentage of component C is 0.1% to 25%;

The optimal weight percentage range of the B component is 0.1%-20%, and the optimal weight percentage range of the C component is 0.1%-10%.

Among them, component A is the original ecological polypropylene resin (referred to as PP). The so-called "original ecological polypropylene resin" is a polypropylene resin directly produced from the polymerization kettle without adding any additives.

Component B is vinyl polybutadiene with a vinyl content molar ratio of 50% to 98%, preferably vinyl polybutadiene with a vinyl content molar ratio of 70% to 98%.

Component C is acrylates: trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (EO ₃ -TMPTA), propoxylated trimethylolpropane triacrylate ester (PO ₃ -TMPTA), trimethylolpropane trimethacrylate (TMPTMA), propoxylated glycerol triacrylate (PO ₃ -GTA), pentaerythritol triacrylate (PETA), 1,4-butanediol Diacrylate (BDDA) or 1,6-hexanediol diacrylate (HDDA).

The preparation method of the present invention is:

(1) Twin-screw extruder or single-screw extruder is selected for melt grafting reaction equipment; A component, B component and C component are mixed evenly according to the proportion, and extruded from the twin-screw extruder or single-screw extruder The feeding port of the machine is added to the material cavity to carry out the melt grafting reaction. The rotation speed of the twin-screw extruder or single-screw extruder is 20-300 rpm, and the twin-screw extruder or single-screw extruder is divided into There are four heating zones, among which, the temperature of the first heating zone is set at 190°C to 230°C, the temperature of the second heating zone is set at 200°C to 240°C, the temperature of the third heating zone is set at 200°C to 240°C, and the temperature of the fourth heating zone is The temperature is set at 200° C. to 240° C., extruded and granulated to obtain high melt strength polypropylene resin.

(2), melt grafting reaction equipment select internal mixer; A component, B component and C component are mixed uniformly according to proportioning, add to material chamber from the feeding port of internal mixer, carry out melting grafting reaction, The reaction temperature is set at 190° C. to 240° C., the reaction time is 1 to 15 minutes, and the reaction is completed to obtain a high melt strength polypropylene resin.

The test instrument that the present invention adopts in embodiment is as follows:

Tensile performance test: using Inxtron material testing machine, the tensile speed is 50mm/min;

Determination of crystallization temperature: using DSC;

Melt index measurement: using SRZ-400D melt flow rate tester;

Melt strength measurement: adopt RHEOTENS 71.97 melt strength tester.

The invention abandons the traditional method of using peroxide to initiate grafting reaction to prepare high-melt-strength polypropylene resin, and adopts the method of in-situ heat-induced grafting to prepare high-melt-strength polypropylene resin. This method is simple and convenient, without the need to introduce peroxide initiators, and can be directly applied to the modification of ordinary polypropylene resins currently produced to produce high melt strength polypropylene resins, thereby saving manpower, material and financial resources, and improving high efficiency. Market Competitive Position of Melt Strength Polypropylene Resins.

Specific examples are as follows.

Example 1

It is 99.8% by weight to take 2994 grams of polypropylene, and the weight percentage is 0.1%. It is to weigh 3 grams of vinyl polybutadiene with a vinyl content molar ratio of 96%, and it is 0.1% by weight to weigh trimethylolpropane. 3 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set to 20 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 190°C, the temperature of the second heating zone is set at 210°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 2

It is 98% by weight to take 2940 grams of polypropylene, and it is 1% by weight to take 30 grams of vinyl polybutadiene with a vinyl content molar ratio of 96%, and it is 1% by weight to take trimethylolpropane 30 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D = 40 and Φ of 35 mm, the number of revolutions of the extruder was set to 70 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 200°C, the temperature of the third heating zone is set at 200°C, and the temperature of the fourth heating zone is set at 200°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 3

It is 97% by weight to take 2910 grams of polypropylene, and it is 2% by weight to take 60 grams of vinyl polybutadiene with a vinyl content molar ratio of 96%, and it is 1% by weight to take trimethylolpropane 30 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set to 100 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 210°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 4

It is 98% by weight to take 2940 grams of polypropylene, and it is 0.5% by weight to take 15 grams of vinyl polybutadiene with a vinyl content molar ratio of 96%, and it is 1.5% by weight to take trimethylolpropane 45 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set at 150 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 5

It is 97% by weight to take 2910 grams of polypropylene, and it is 1% by weight to take 30 grams of vinyl polybutadiene with a vinyl content molar ratio of 93%, and it is 2% by weight to take trimethylolpropane 60 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 220°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 6

It is 95% by weight to take 2850 grams of polypropylene, and the weight percentage is 4.9% to weigh 147 grams of vinyl polybutadiene with a vinyl content molar ratio of 93%, and it is 0.1% by weight to take trimethylolpropane 3 grams of trimethacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set at 250 revolutions per minute, and extruded The machine is divided into four heating zones, the temperature of the first heating zone is set at 190°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 240°C. Extrusion granulation to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 7

It is 96% by weight to take 2880 grams of polypropylene, and it is 2% by weight to take 60 grams of vinyl polybutadiene with a vinyl content molar ratio of 96%, and it is 2% by weight to take trimethylolpropane 60 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set to 300 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 190°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 240°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 8

Be 95% by weight to take 2850 grams of polypropylene, 2% by weight to take 60 grams of vinyl polybutadiene with a vinyl content molar ratio of 93%, and take 3% by weight to take trimethylolpropane 90 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 210°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 9

Be 94.99% by weight and take 2850 grams of polypropylene, 3 percent by weight, take 90 grams of vinyl polybutadiene with a vinyl content molar ratio of 93 percent, and take 2 percent by weight of trimethylolpropane 60 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 230°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 10

It is 90% by weight to take 2700 grams of polypropylene, and it is 3% by weight to take 90 grams of vinyl polybutadiene with a vinyl content molar ratio of 91%, and it is 7% by weight to take trimethylolpropane 210 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to an internal mixer for melt grafting reaction, the temperature was set at 210°C, and after 1 minute of melt reaction, the reaction was terminated to obtain a high melt strength polypropylene resin . Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 11

It is 90% by weight to take 2700 grams of polypropylene, and it is 7% by weight to take 210 grams of vinyl polybutadiene with a vinyl content molar ratio of 98%, and it is 3% by weight to take trimethylolpropane 90 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the rotation number of the extruder was set to 210 rpm, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 240°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 240°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 12

Be 85% by weight to take 2550 grams of polypropylene, 5% by weight to take 150 grams of vinyl polybutadiene with a vinyl content molar ratio of 91%, and take 10% by weight to take trimethylolpropane 300 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 13

It is 85% by weight to take 2550 grams of polypropylene, and 10% by weight is to weigh 300 grams of vinyl polybutadiene with a vinyl content molar ratio of 91%, and it is 5% by weight to take trimethylolpropane 150 grams of triacrylate, mixed uniformly in the mixer for 20 minutes, then added to the internal mixer for melt grafting reaction, the temperature was set at 190 ° C, after 15 minutes of melt reaction, the reaction was terminated to obtain high melt strength polypropylene resin . Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 14

Be 80% by weight to take 2400 grams of polypropylene, 10% by weight to take 300 grams of vinyl polybutadiene with a vinyl content molar ratio of 98%, and take 10% by weight to take trimethylolpropane 300 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to an internal mixer for melt grafting reaction, the temperature was set at 240°C, and after 10 minutes of melt reaction, the reaction was terminated to obtain a high melt strength polypropylene resin . Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 15

It is 75% by weight to take 2250 grams of polypropylene, and 10% by weight is to weigh 300 grams of vinyl polybutadiene with a vinyl content molar ratio of 91%, and it is 15% by weight to take trimethylolpropane 450 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 230°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 16

Be 70% by weight to take 2100 grams of polypropylene, 5% by weight to take 150 grams of vinyl polybutadiene with a vinyl content molar ratio of 91%, and take 25% by weight to take trimethylolpropane 750 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set at 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 17

It is 79.9% by weight to take 2397 grams of polypropylene, and it is 20% by weight to take 600 grams of vinyl polybutadiene with a vinyl content molar ratio of 90%, and it is 0.1% by weight to take propoxylated glycerin triacrylic acid 3 grams of ester, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D = 40 and Φ of 35 mm, the number of revolutions of the extruder was set at 200 revolutions per minute, and the extruder was divided into Four heating zones, the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 230°C, the temperature of the fourth heating zone is set at 220°C, extrusion granulation , to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 18

It is 84.9% by weight and weighs 2547 grams of polypropylene, and the weight percentage is 0.1%. It weighs 3 grams of vinyl polybutadiene with a vinyl content molar ratio of 90%, and it is 15% by weight. Take trimethylolpropane 450 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 190°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 19

Be 95% by weight to take 2850 grams of polypropylene, 2.5% by weight to weigh 75 grams of vinyl polybutadiene with a vinyl content molar ratio of 87%, and take 2.5% by weight to take trimethylolpropane 75 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set at 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 220°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 20

It is 96% by weight to take 2880 grams of polypropylene, and it is 1% by weight to take 30 grams of vinyl polybutadiene with a vinyl content molar ratio of 85%, and it is 3% by weight to take trimethylolpropane 90 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a single-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set to 20 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 190°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 200°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 21

It is 94% by weight to take 2820 grams of polypropylene, and it is 3% by weight to take 90 grams of vinyl polybutadiene with a vinyl content molar ratio of 82%, and it is 3% by weight to take trimethylolpropane 90 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a single-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set to 100 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 210°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 210°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 22

It is 97% by weight to take 2910 grams of polypropylene, and it is 1% by weight to take 30 grams of vinyl polybutadiene with a vinyl content molar ratio of 76%, and it is 2% by weight to take trimethylolpropane 60 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a single-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 240°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 23

It is 92% by weight to take 2760 grams of polypropylene, and it is 2% by weight to take 60 grams of vinyl polybutadiene with a vinyl content molar ratio of 74%, and it is 6% by weight to take 1,4-butane 180 grams of diol diacrylate, mixed uniformly in a mixer for 20 minutes, then added to a single-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set at 300 revolutions per minute, and extruded The machine is divided into four heating zones, the temperature of the first heating zone is set at 230°C, the temperature of the second heating zone is set at 240°C, the temperature of the third heating zone is set at 240°C, and the temperature of the fourth heating zone is set at 240°C. Extrusion granulation to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 24

It is 89% by weight to take 2670 grams of polypropylene, and it is 3% by weight to take 90 grams of vinyl polybutadiene with a vinyl content molar ratio of 70%, and it is 8% by weight to take 1,6-hexyl 240 grams of diol diacrylate, uniformly mixed in the mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set at 220 revolutions per minute, extruded The machine is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 210°C. Extrusion granulation to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 25

It is 93% by weight to take 2790 grams of polypropylene, and it is 3% by weight to take 90 grams of vinyl polybutadiene with a vinyl content molar ratio of 66%, and it is 4% by weight to weigh pentaerythritol triacrylate 120 gram, mixed uniformly in the mixer for 20min, then added to the twin-screw extruder with L/D=40 and Φ of 35mm, the rotation number of the extruder was set at 120 rpm, and the extruder was divided into four Heating zones, wherein the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 210°C, extruded and granulated to obtain High melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1.

Example 26

It is 94% by weight to take 2820 grams of polypropylene, and it is 4% by weight to take 120 grams of vinyl polybutadiene with a vinyl content molar ratio of 65%, and it is 2% by weight to take trimethylolpropane 60 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 210°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 210°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1

Example 27

It is 88% by weight to take 2640 grams of polypropylene, and it is 6 percent by weight to take 180 grams of vinyl polybutadiene with a vinyl content molar ratio of 63%, and it is 6 percent by weight to take trimethylolpropane 180 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, the number of revolutions of the extruder was set to 200 revolutions per minute, and the extruder It is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 230°C, the temperature of the third heating zone is set at 230°C, and the temperature of the fourth heating zone is set at 210°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1

Example 28

It is 88% by weight to take 2640 grams of polypropylene, and 2% by weight is to weigh 60 grams of vinyl polybutadiene with vinyl content molar ratio of 55%, and it is 10% by weight to take propoxylated three 300 grams of methylolpropane triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, and the rotation number of the extruder was set at 100 rpm , The extruder is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 210°C ℃, extruded and granulated to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1

Example 29

It is 88% by weight to take 2640 grams of polypropylene, and it is 8% by weight to take 240 grams of vinyl polybutadiene with a vinyl content molar ratio of 50%, and it is 4% by weight to take ethoxylated tri 120 grams of methylolpropane triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35mm, and the rotation number of the extruder was set at 200 rpm , The extruder is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 210°C ℃, extruded and granulated to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1

Example 30

It is 85% by weight to take 2550 grams of polypropylene, and 10% by weight is to weigh 300 grams of vinyl polybutadiene with a vinyl content molar ratio of 50%, and it is 5% by weight to take trimethylolpropane 150 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the rotation number of the extruder was set at 180 rpm, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 210°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1

Example 31

It is 95% by weight to take 2850 grams of polypropylene, and 2% by weight is to weigh 60 grams of vinyl polybutadiene with a vinyl content molar ratio of 91%, and it is 3% by weight to weigh 1,6-hexyl 90 grams of diol diacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the number of revolutions of the extruder was set at 200 revolutions per minute, and extruded The machine is divided into four heating zones, the temperature of the first heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 210°C. Extrusion granulation to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1

Example 32

It is 70% by weight to take 2100 grams of polypropylene, and it is 29.9% by weight to take 897 grams of vinyl polybutadiene with a vinyl content molar ratio of 91%, and it is 0.1% by weight to take trimethylolpropane 3 grams of triacrylate, mixed uniformly in a mixer for 20 minutes, then added to a twin-screw extruder with L/D=40 and Φ of 35 mm, the rotation number of the extruder was set to 200 rpm, and the extruder It is divided into four heating zones, the temperature of one heating zone is set at 200°C, the temperature of the second heating zone is set at 220°C, the temperature of the third heating zone is set at 220°C, and the temperature of the fourth heating zone is set at 210°C. Pelletizing to obtain high melt strength polypropylene resin. Some samples were taken for performance testing and melt strength determination. The results are shown in Table 1

The test result of table 1 embodiment 1～32

serial number Tensile strength (MPa) Tensile modulus (MPa) Elongation at break (%) Crystallization temperature (°C) Melt index (g/10min) Melt strength (cN) Pure polypropylene 38 700 762 110 2.28 5 Example 1 38 720 701 111 2.07 8 Example 2 38 744 690 113 1.78 11 Example 3 39 790 670 118 1.51 20 Example 4 38 750 680 114 1.71 13 Example 5 39 812 662 124 0.66 31

Example 6 39 781 672 117 1.65 16 Example 7 40 823 659 120 1.14 25 Example 8 40 832 641 127 0.41 42 Example 9 39 811 660 125 0.56 35 Example 10 41 841 629 122 1.07 27 Example 11 41 804 671 123 0.69 30 Example 12 42 852 641 120 1.12 twenty four Example 13 40 833 640 124 0.60 32 Example 14 42 867 622 127 0.45 37 Example 15 42 871 619 119 1.33 twenty two Example 16 41 970 607 122 1.01 28 Example 17 41 710 708 123 0.70 30 Example 18 39 849 635 127 0.43 39 Example 19 39 801 680 124 0.57 33 Example 20 38 829 645 122 1.05 27 Example 21 39 805 673 124 0.66 31 Example 22 38 785 691 120 1.08 26 Example 23 38 766 692 119 1.41 twenty one Example 24 38 780 688 119 1.35 twenty two Example 25 37 791 675 123 0.71 30 Example 26 39 775 689 118 1.45 20 Example 27 38 740 691 120 1.30 twenty three Example 28 39 732 699 124 0.63 32 Example 29 38 710 703 122 0.72 29 Example 30 37 768 692 120 1.40 twenty one Example 31 39 822 655 123 0.67 30 Example 32 40 835 632 124 0.65 31

Claims (6)

1, high bath strength acrylic resin, it is made up of A component, B component and C component: wherein the weight percent of A component is 70%～99.8%, and the weight percent of B component is 0.1%～29.9%, and the weight percent of C component is 0.1%～25%;

Described A component is the ecosystem acrylic resin; The acrylic resin of ecosystem acrylic resin for not adding any auxiliary agent, coming out by direct production in the polymeric kettle;

The B component is 50%～98% vinyl polybutadiene for the contents of ethylene molar ratio;

The C component is an esters of acrylic acid: Viscoat 295, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295, trimethylolpropane trimethacrylate, glycerol propoxylate triacrylate, pentaerythritol triacrylate, 1,4-butylene glycol diacrylate or 1,6 hexanediol diacrylate;

2, high bath strength acrylic resin according to claim 1 is characterized in that, the scope of the weight percent of described B component is 0.1%～20%.

3, high bath strength acrylic resin according to claim 1 is characterized in that, the scope of the weight percent of described C component is 0.1%～10%.

5, high bath strength acrylic resin according to claim 1 is characterized in that, described B component is 70%～98% vinyl polybutadiene for selection contents of ethylene molar ratio.

6, the preparation method of high bath strength acrylic resin according to claim 1 is characterized in that, step and condition are:

Melting graft reaction equipment is chosen twin screw extruder or single screw extrusion machine; With the A component, B component and C component mix by proportioning, join the material chamber from the spout of twin screw extruder or single screw extrusion machine, carry out melting graft reaction, twin screw extruder or single screw extrusion machine revolution are set at 20 rev/mins～300 rev/mins, it is four heating zone that twin screw extruder or single screw extrusion machine are divided into, wherein, one Heating Zone Temperature is set at 190 ℃～230 ℃, two Heating Zone Temperature are set at 200 ℃～240 ℃, three Heating Zone Temperature are set at 200 ℃～240 ℃, four Heating Zone Temperature are set at 200 ℃～240 ℃, and extruding pelletization obtains high bath strength acrylic resin.

7, the preparation method of high bath strength acrylic resin according to claim 1 is characterized in that, step and condition are:

Melting graft reaction equipment is chosen Banbury mixer; A component, B component and C component are mixed by proportioning, join the material chamber, carry out melting graft reaction from the spout of Banbury mixer, temperature of reaction is set at 190 ℃～240 ℃, reaction times is 1～15 minute, finishes reaction, obtains high bath strength acrylic resin.