CN104250394B - A kind of modified polypropylene material and preparation method thereof - Google Patents

Abstract

The present invention provides a kind of modified polypropylene material and preparation method thereof, is prepared from by 100 parts of polypropylene, 0.01 0.05 parts of antioxidant 1425,0.01 0.05 parts of antioxidant 619,0.01 0.05 parts of antioxidant 1035,0 100 parts of fillers, 01 parts of lubricants, 01 parts of coupling agents, 0 30 parts of toughener.Three kinds of combination antioxidant are added in the present invention to be modified polypropylene material, improve polyacrylic hydrolysis, ageing resistace, mechanical stability and colour stability of the material in higher processing temperature or temperature in use can be kept for a long time.And antioxidant total addition level is reduced, so as to save polyacrylic modified cost.

Description

A kind of modified polypropylene material and preparation method thereof

technical field

The invention belongs to the field of polymer materials, and in particular relates to a modified polypropylene material and a preparation method thereof.

Background technique

During the processing and use of plastic products, plastic polymers will be degraded to varying degrees due to factors such as heat and oxygen, which will directly have a negative impact on the physical properties, mechanical properties, appearance, color, and use functions of resins and products. At present, the use of antioxidants is one of the methods to effectively delay the degradation or thermo-oxidative aging of resins and products.

Many parts made of polypropylene plastic injection molding are thin-walled parts, with a thickness of only about 2mm. In some applications, they need to have properties such as hydrolysis resistance and long-term resistance to thermal and oxidative aging. Some commonly used antioxidants such as tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester (common name antioxidant 1010), 1,3,5-tri(3 , 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (common name antioxidant 3114), tris[2.4-di-tert-butylphenyl] phosphite (common name antioxidant 168), di Pentaerythritol distearyl phosphite (common name antioxidant 618), bis(octadecyl)thiodipropionate (common name antioxidant DSTP) etc. are used to modify polypropylene material to improve its hydrolysis resistance, Aging resistance performance, but it is difficult for them to be used alone or compound with each other to meet the requirements of polypropylene material parts in special occasions.

Contents of the invention

The purpose of the present invention is to provide a modified polypropylene material capable of hydrolysis resistance and long-term resistance to heat and oxygen aging and a preparation method thereof.

The technical solution of the present invention is: a modified polypropylene material prepared from the following components in parts by weight:

Polypropylene 100 parts

Bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium (common name Antioxidant 1425) 0.01-0.05 parts

Pentaerythritol distearyl diphosphite (common name Antioxidant 619) 0.02-0.05 parts

Thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (common name Antioxidant 1035) 0.01-0.05 parts

Further, the filler is glass fiber and/or talcum powder.

Further, the lubricant is paraffin.

The coupling agent is a silane coupling agent 3-aminopropyltriethoxysilane (common name KH550).

The toughening agent is ethylene-octene copolymer (common name POE).

Another object of the present invention is to provide a method for preparing modified polypropylene materials: mix 100 parts of polypropylene, 0.01-0.05 parts of bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) Calcium (antioxidant 1425), 0.02-0.05 parts of pentaerythritol distearyl diphosphite (antioxidant 619), 0.01-0.05 parts of thiodiethylenebis[3-(3,5-di-tert-butyl -4-hydroxyphenyl) propionate] (antioxidant 1035), 0-100 parts of filler, 0-1 part of lubricant, 0-1 part of coupling agent, 0-30 parts of toughening agent are mixed evenly, Add it into the feeding port of the extruder, the melting temperature is 150-230°C, and then extrude and granulate to obtain the modified polypropylene material.

Among them, the chemical name of antioxidant 1425: bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium, the chemical name of antioxidant 619: pentaerythritol distearyl diphosphite, Antioxidant 1035 Chemical name: Thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

Beneficial effects of the present invention:

1. In the present invention, the combined antioxidant composed of antioxidant 1425, antioxidant 619 and antioxidant 1035 is added to modify the polypropylene material, which improves the hydrolysis resistance and aging resistance of polypropylene

2. The total addition amount of the combined antioxidant of the present invention is 0.04-0.15 parts by weight, which is very small and is 1/10 of that of ordinary antioxidants, which greatly saves the modification cost of polypropylene.

3. The modified polypropylene material of the present invention has remarkable anti-hydrolysis and anti-high-temperature oxidation effects, and can maintain the mechanical stability and color stability of the material at a relatively high processing temperature or service temperature for a long time.

detailed description

The preparation method of each specific embodiment in the present invention is the general extrusion process of extruder: 100 parts of polypropylene, 0.1-0.5 parts of compound antioxidant, 0-100 parts of filler, 0-1 part of lubricant, 0 - After mixing 1 part of coupling agent and 0-30 parts of toughening agent evenly, add it to the feed port of the extruder, melt at a temperature of 150-230°C, and extrude to granulate.

The present invention adopts following detection method to carry out tensile strength, unnotched impact strength, anti-hydrolysis sample aging time to carry out performance test to the prepared modified polypropylene material sample, and each test standard is as follows:

1. The tensile strength test standard adopts the ASTM-D638 standard of the American Society for Experimental Materials, and the tensile speed is 5mm/min. The test splines are divided into five groups:

In the first group, the splines were naturally cooled for 24 hours for testing.

In the second group, the splines were first boiled for 1600 hours, and then subjected to thermal oxygen aging for 120 hours before performance testing.

In the third group, the splines were first boiled for 1600 hours, and then subjected to thermal oxygen aging for 720 hours before performance testing.

In the fourth group, the splines were first boiled for 3200 hours, and then subjected to thermal oxygen aging for 120 hours before performance testing.

In the fifth group, the splines were first boiled for 3200 hours, and then subjected to thermal oxygen aging for 720 hours before performance testing.

2. The impact performance test standard adopts the ASTM-D256 standard of the American Society for Testing and Materials. The test splines are divided into five groups:

In the first group, the splines were naturally cooled for 24 hours for testing.

In the second group, the splines were first boiled for 1600 hours, and then subjected to thermal oxygen aging for 120 hours before performance testing.

In the third group, the splines were first boiled for 1600 hours, and then subjected to thermal oxygen aging for 720 hours before performance testing.

In the fourth group, the splines were first boiled for 3200 hours, and then subjected to thermal oxygen aging for 120 hours before performance testing.

In the fifth group, the splines were first boiled for 3200 hours, and then subjected to thermal oxygen aging for 720 hours before performance testing.

3. Test standard for hydrolysis resistance: immersion in pure water, water temperature 95°C, boiling time 1600h, 3200h.

The thermal oxygen aging performance of the material is carried out according to ISO-4577, the thickness of the sample is 2mm, and the set temperature is 150°C.

The tests are divided into two groups:

In the first group, the splines were first boiled in water for 1600 hours, and passed through an oven set at 150°C until the material was pulverized.

In the second group, the splines were first boiled in water for 3200 hours, and passed through an oven set at 150°C until the material was pulverized.

Example 1:

Components of a modified polypropylene material:

Preparation method: Mix 100 parts of polypropylene, 0.01 part of antioxidant 1425, 0.02 part of antioxidant 619, 0.01 part of antioxidant 1035, 50 parts of glass fiber, 1 part of paraffin, and 1 part of coupling agent KH550, and then add In the feeding port of the extruder, the melting temperature is 150-230°C, and then extruded and granulated to obtain a modified polypropylene material. Example 2:

Components of a modified polypropylene material:

Preparation method: 100 parts of polypropylene, 0.05 parts of antioxidant 1425, 0.05 parts of antioxidant 619, 0.02 parts of antioxidant 1035, 50 parts of glass fiber, 50 parts of talcum powder, 1 part of paraffin, 1 part of coupling agent KH550 , 30 parts of POE are mixed evenly, and then added to the feed port of the extruder, the melting temperature is 150-230°C, and then extruded and granulated to obtain a modified polypropylene material.

Example 3:

Components of a modified polypropylene material:

Preparation method: After mixing 100 parts of polypropylene, 0.02 parts of antioxidant 1425, 0.04 parts of antioxidant 619, and 0.05 parts of antioxidant 1035, add them to the feed port of the extruder, and the melting temperature is 150-230 ° C. Then Modified polypropylene material is obtained by extrusion granulation.

Example 4:

Components of a modified polypropylene material:

Preparation method: Mix 100 parts of polypropylene, 0.04 part of antioxidant 1425, 0.04 part of antioxidant 619, 0.01 part of antioxidant 1035, 30 parts of glass fiber, 0.5 part of paraffin, 0.5 part of coupling agent KH550, and 10 parts of POE. , added to the feed port of the extruder, the melting temperature is 150-230 ° C, and then extruded and granulated to obtain a modified polypropylene material.

Example 5:

Components of a modified polypropylene material:

Preparation method: mix 100 parts of polypropylene, 0.03 parts of antioxidant 1425, 0.05 parts of antioxidant 619, 0.04 parts of antioxidant 1035, 20 parts of talc, 0.2 parts of paraffin, 1 part of coupling agent KH550, and 20 parts of POE After uniformity, it is added to the feed port of the extruder, the melting temperature is 150-230°C, and then extruded and granulated to obtain a modified polypropylene material.

In order to compare its water resistance, thermal oxygen resistance and aging resistance with the polypropylene material of the general antioxidant system, based on Example 1, and under the condition of the same process, the antioxidant in the formula was replaced with a common antioxidant to form a comparative example 1-4, specifically as follows:

Comparative example 1:

Components of a modified polypropylene material:

Preparation method: Mix 100 parts of polypropylene, 0.2 parts of antioxidant 1010, 0.4 parts of antioxidant 168, 50 parts of glass fiber, 1 part of paraffin, and 1 part of coupling agent KH550, and then add it to the feed port of the extruder. The melting temperature is 150-230°C, and then extruded and granulated to obtain a modified polypropylene material.

Comparative example 2:

Components of a modified polypropylene material:

Preparation method: Mix 100 parts of polypropylene, 0.3 part of antioxidant 3114, 0.1 part of antioxidant 618, 0.3 part of antioxidant DSTP, 50 parts of glass fiber, 1 part of paraffin, and 1 part of coupling agent KH550, then add In the feeding port of the extruder, the melting temperature is 150-230°C, and then extruded and granulated to obtain a modified polypropylene material.

Comparative example 3:

Components of a modified polypropylene material:

Preparation method: Mix 100 parts of polypropylene, 0.1 part of antioxidant 1010, 0.3 part of antioxidant 618, 50 parts of glass fiber, 1 part of paraffin, and 1 part of coupling agent KH550, and then add it to the feed port of the extruder. The melting temperature is 150-230°C, and then extruded and granulated to obtain a modified polypropylene material.

Comparative example 4:

Components of a modified polypropylene material:

Preparation method: Mix 100 parts of polypropylene, 0.3 part of antioxidant 3114, 0.1 part of antioxidant 618, 0.5 part of antioxidant DSTP, 50 parts of glass fiber, 1 part of paraffin, and 1 part of coupling agent KH550, then add In the feeding port of the extruder, the melting temperature is 150-230°C, and then extruded and granulated to obtain a modified polypropylene material.

The formula and test data of above-mentioned embodiment 1-5 and comparative example 1-4 are shown in the following table one:

Table I:

It can be seen from the above table: (1) The amount of antioxidant added in the modified polypropylene material prepared by the present invention is 0.04-0.15 parts, while the amount of common antioxidant used in Comparative Examples 1-4 is 0.4-0. 0.9 servings. Therefore, the amount of antioxidant used in the present invention is very small, which is only about 1/10 of the amount of antioxidant used in the prior art, so that the modification cost of polypropylene material can be greatly saved.

(2) The anti-aging performance of the modified polypropylene material prepared by the present invention is obviously higher than that of the comparative example.

(3) Comparing the mechanical properties of Example 1 and Comparative Examples 1-4 of the same formulation system: the tensile and unnotched impact strength of the modified polypropylene material prepared in Example 1 was obtained after the material was boiled for 1600h + thermal oxygen aging for 120h or water After boiling for 3200h + thermal oxygen aging for 120h, the performance can still maintain more than 85% of the original performance, while the performance of the four comparative products drops below 30% of the original performance; after boiling for 1600h + thermal oxygen aging for 720h or boiling for 3200h + thermal oxygen After aging for 720h, the performance of the product in Example 1 can still maintain more than 60% of the original performance, while the performance of the four comparative products has been pulverized, and the mechanical properties are 0; in the aging experiment, the product in Example 1 is pulverized The time is more than 49 days, while the pulverization time of the four comparative examples is 3-11 days. Therefore, compared with the ordinary anti-oxidation system polypropylene material, the modified polypropylene material prepared by the present invention has remarkable anti-hydrolysis and anti-high temperature oxidation effects, and can maintain the mechanical stability of the material at a higher processing temperature or service temperature for a long time. It is far better than the antioxidant effect brought by the use of general antioxidant systems.

The above embodiments are not limited to the protection scope of the present invention, and all modifications or variations based on the basic idea of the present invention belong to the protection scope of the present invention.

Claims (5)

1. a kind of modified polypropylene material, it is characterised in that：It is prepared from by weight by following component：

100 parts of polypropylene

Double (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) 0.01-0.05 parts of calcium

0.02-0.05 parts of diphosphorous acid pentaerythrite distearyl alcohol ester

0.01-0.05 parts of thio diethylene double [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic esters]

0-100 parts of filler

0-1 parts of lubricant

0-1 parts of coupling agent

0-30 parts of toughener,

100 parts of polypropylene, 0.01-0.05 parts of double (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) calcium, 0.02- 0.05 part of diphosphorous acid pentaerythrite distearyl alcohol ester, the double [3- (3,5- di-t-butyl -4- hydroxyls of 0.01-0.05 parts of thio diethylenes Base phenyl) propionic ester], 0-100 parts of fillers, 0-1 parts of lubricants, 0-1 parts of coupling agents, 0-30 parts of toughener it is well mixed after, plus Enter to extrude in machine inlet, melting temperature is 150-230 DEG C, then extruding pelletization obtains modified polypropylene material.

2. a kind of modified polypropylene material according to claim 1, it is characterised in that：Described filler is glass fibre And/or talcum powder.

3. a kind of modified polypropylene material according to claim 1, it is characterised in that：Described lubricant is paraffin.

4. a kind of modified polypropylene material according to claim 1, it is characterised in that：Described coupling agent is silane coupled Agent 3- aminopropyl triethoxysilanes.

5. a kind of modified polypropylene material according to claim 1, it is characterised in that：Described toughener is ethene-pungent Alkene copolymer.