阅读说明：本技术 一种聚烯烃材料及其制备方法和应用 (Polyolefin material and preparation method and application thereof ) 是由 赵治国 黄险波 叶南飚 杨霄云 陆湛泉 于 2020-12-22 设计创作，主要内容包括：本发明公开了一种聚烯烃材料及其制备方法和应用,包括组分：增强纤维母粒90-99.9份；引发剂母粒0.1-10份。本发明通过增强纤维母粒和引发剂母粒共混,增强纤维母粒使得产品的强度得到进一步提高,引发剂母粒利用低熔点聚烯烃树脂,避免了引发剂在加工过程中反应,有机过氧化物引发剂使聚乙烯发生部分交联,形成的微交联结构不仅使产品的强度进一步提高,且短期耐热性和长期耐热性得到明显改善,使材料适用于对强度和耐热性同时需求的场合。(The invention discloses a polyolefin material and a preparation method and application thereof, wherein the polyolefin material comprises the following components: 90-99.9 parts of reinforced fiber master batch; 0.1-10 parts of initiator master batch. According to the invention, the strength of the product is further improved by the reinforced fiber master batch and the initiator master batch through blending, the initiator master batch utilizes the low-melting-point polyolefin resin, the reaction of the initiator in the processing process is avoided, the organic peroxide initiator enables the polyethylene to be partially crosslinked, the formed micro-crosslinking structure not only enables the strength of the product to be further improved, but also obviously improves the short-term heat resistance and the long-term heat resistance, and the material is suitable for occasions requiring the strength and the heat resistance at the same time.)

1. The polyolefin material is characterized by comprising the following components in parts by weight:

90-99.9 parts of reinforced fiber master batch;

0.1-10 parts of initiator master batch;

the reinforced fiber master batch comprises the following components in parts by weight:

15-95 parts of polyethylene resin;

5-60 parts of reinforcing fiber;

0.5-10 parts of a compatilizer;

the initiator master batch comprises the following components in parts by weight:

10-99 parts of low-melting-point polyolefin resin;

0.1-50 parts of initiator.

2. The polyolefin material according to claim 1, wherein the polyethylene resin is selected from one or more of low density polyethylene, linear low density polyethylene and high density polyethylene.

3. The polyolefin material according to claim 1, wherein the compatibilizer is a graft polymer of a polar monomer and polyethylene, wherein the polar monomer is one or more selected from maleic anhydride, acrylic acid and acrylate derivatives.

4. Polyolefin material according to claim 1, wherein the reinforcing fibers are selected from one or a mixture of several of glass fibers, quartz fibers and basalt fibers, preferably glass fibers.

5. The polyolefin material according to claim 1, wherein the low-melting polyolefin resin is a polyolefin material with a melting point lower than 150 ℃, and is selected from one or a mixture of EVA, POE or LLDPE resins.

6. The polyolefin material of claim 1, wherein the initiator is an organic peroxide initiator selected from dicetyl bis (2, 4-dichlorobenzoyl) peroxydicarbonate, ditetradecyl peroxydicarbonate, dibutyl peroxydicarbonate, 1,3, 3-tetramethylbutyl peroxypivalate, teropentyl peroxypivalate, t-butyl peroxypivalate, bis (3,3, 5-trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, diisobutyryl peroxide, isopropylphenyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, teropentyl peroxyneodecanoate, and mixtures thereof, Tert-butyl peroxyneodecanoate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoylperoxy) hexane, 1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate, bis (4-methylbenzoyl) peroxide, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, 1-di-tert-amylperoxycyclohexane, 1-di-tert-butylperoxycyclohexane, di-butylperoxydiisopropylcyclohexane, di-tert-butylperoxycyclohexane, Tert-butyl peroxyisononanoate, tert-amyl peroxyacetate, tert-amyl peroxy (2-ethylhexyl) carbonate, 2-di (tert-butylperoxy) butane, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, 4-bis (tert-butylperoxy) valerate, tert-butyl peroxybenzoate, ditert-amyl peroxide, dicumyl peroxide, bis (tert-butylperoxyisopropyl) benzene, 2, 5-di-tert-butylperoxy-2, 5-dimethylhexane, tert-butylperoxycumene, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexyne-3, di-tert-butyl peroxide, tert-butyl peroxide, One or more of p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,3, 3-tetramethyl butyl hydroperoxide, cumene hydroperoxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, methyl ethyl ketone peroxide or acetylacetone peroxide.

7. Process for the preparation of a polyolefin material according to any one of claims 1 to 6, characterized in that it comprises the following steps:

(1) mixing polyethylene resin and a compatilizer according to a ratio, adding the mixture into a main feeding system of an extruder, adding the reinforced fiber into a side feeding system, and mixing, extruding and granulating all the components through the extruder to obtain reinforced fiber master batches;

(2) adding the low-melting-point polyolefin resin and the initiator into a main feeding system of an extruder according to the proportion, mixing, extruding and granulating to prepare initiator master batches;

(3) and blending the reinforced fiber master batch and the initiator master batch to obtain the polyolefin material.

8. Use of a polyolefin material according to any of claims 1 to 6 in the field of household appliances, construction or communication.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a polyolefin material, and a preparation method and application thereof.

Background

Polyethylene is a thermoplastic resin obtained by polymerizing ethylene. In industry, copolymers of ethylene with small amounts of alpha-olefins are also included. The polyethylene is odorless and nontoxic, feels like wax, has excellent low-temperature resistance (the lowest use temperature can reach-100 to-70 ℃), has good chemical stability, and can resist corrosion of most of acid and alkali (cannot resist acid with oxidation property). Is insoluble in common solvents at room temperature, has low water absorption and excellent electrical insulation. Polyethylene is widely used, mainly for producing films, packaging materials, containers, pipes, monofilaments, electric wires and cables, daily necessities and the like, and can be used as a high-frequency insulating material for televisions, radars and the like.

However, the mechanical properties of the polyethylene resin are very low and the heat distortion temperature is also low. At present, the conventional method for effectively improving the mechanical property and the heat distortion temperature of polyethylene is to add glass fiber for reinforcement, but the method does not obviously improve the mechanical property and the heat resistance of the polyethylene material.

Therefore, it is necessary to research a polyethylene material having both high strength and high heat resistance to satisfy the simultaneous requirements of strength and heat resistance.

Disclosure of Invention

In order to overcome the above-mentioned drawbacks of the prior art, the primary object of the present invention is to provide a polyolefin material having significantly improved mechanical properties and heat resistance.

Another object of the present invention is to provide a process for preparing the above polyolefin material.

The invention is realized by the following technical scheme:

the polyolefin material comprises the following components in parts by weight:

90-99.9 parts of reinforced fiber master batch;

0.1-10 parts of initiator master batch;

the reinforced fiber master batch comprises the following components in parts by weight:

15-95 parts of polyethylene resin;

5-60 parts of reinforcing fiber;

0.5-10 parts of a compatilizer;

preferably, the polyethylene resin is selected from one or a mixture of several of low density polyethylene, linear low density polyethylene and high density polyethylene.

Preferably, the compatilizer is a graft polymer of polar monomer and polyethylene, wherein the polar monomer is one or a mixture of more of maleic anhydride, acrylic acid and acrylate derivatives.

Preferably, the reinforcing fiber is one or a mixture of several of glass fiber, quartz fiber and basalt fiber, and is preferably glass fiber.

The initiator master batch comprises the following components in parts by weight:

10-99 parts of low-melting-point polyolefin resin;

0.1-50 parts of initiator.

The initiator and the low-melting-point polyethylene resin are made into master batches, so that the problem of initiator layering is avoided, the performance stability is ensured, and the organic peroxide initiator enables the polyethylene to be partially crosslinked, so that the formed micro-crosslinked structure not only enables the strength of the product to be further improved, but also obviously improves the short-term heat resistance and the long-term heat resistance.

Preferably, the low-melting polyolefin resin is a polyolefin material with a melting point lower than 150 ℃, and is selected from one or a mixture of more of EVA, POE and LLDPE resins.

Preferably, the initiator is an organic peroxide initiator selected from dicetyl peroxybis (2, 4-dichlorobenzoyl) peroxydicarbonate, ditetradecyl peroxydicarbonate, dibutyl peroxydicarbonate, 1,3, 3-tetramethylbutyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, bis (3,3, 5-trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, diisobutyryl peroxide, cumyl peroxyneodecanoate, bis (3-methoxybutyl) peroxydicarbonate, bis (ethoxyhexyl) peroxydicarbonate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, bis (2-ethylhexyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, and mixtures thereof, Bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoylperoxide) hexane, 1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate, bis (4-methylbenzoyl) peroxide, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, 1-dipentylperoxycyclohexane, 1-di-tert-butylperoxycyclohexane, tert-butyl peroxyisononanoate, tert-amyl peroxyacetate, tert-amyl peroxy (2-ethylhexyl) carbonate, diisopropyl peroxydicarbonate, 2, 5-dimethyl-2, 5-ethyl hexanoylperoxide, di-tert-butylperoxy, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexano, 2, 2-di (t-butylperoxy) butane, t-butylperoxy maleate, t-butylperoxy isopropylcarbonate, t-butylperoxy-2-ethylhexyl carbonate, t-amyl peroxybenzoate, t-butylperoxy acetate, butyl 4, 4-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, ditert-amyl peroxide, dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, 2, 5-di-t-butylperoxy-2, 5-dimethylhexane, t-butylperoxycumene, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexyne-3, di-t-butylperoxide, p-menthane hydroperoxide, dicumyl hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, hydrogen peroxide, One or more of tert-amyl hydroperoxide, tert-butyl hydroperoxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, methyl ethyl ketone peroxide or acetylacetone peroxide.

The invention also provides a preparation method of the polyolefin material, which comprises the following steps:

(1) mixing polyethylene resin and a compatilizer according to a ratio, adding the mixture into a main feeding system of an extruder, adding the reinforced fiber into a side feeding system, and mixing, extruding and granulating all the components through the extruder to obtain reinforced fiber master batches;

(2) adding the low-melting-point polyolefin resin and the initiator into a main feeding system of an extruder according to the proportion, mixing, extruding and granulating to prepare initiator master batches;

(3) and blending the reinforced fiber master batch and the initiator master batch to obtain the polyolefin material.

The invention also provides the application of the polyolefin material in the fields of household appliances, buildings or communication.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, the strength of the product is further improved by the reinforced fiber master batch and the initiator master batch through blending, the initiator master batch utilizes the low-melting-point polyolefin resin, the reaction of the initiator in the processing process is avoided, the organic peroxide initiator enables the polyethylene to be partially crosslinked, the formed micro-crosslinking structure not only enables the strength of the product to be further improved, but also obviously improves the short-term heat resistance and the long-term heat resistance, and the material is suitable for occasions requiring the strength and the heat resistance at the same time.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.

The raw materials used in the present invention are commercially available, and the raw materials used in the examples and comparative examples are described below, but not limited to:

polyethylene resin:

high density polyethylene HDPE 5000S;

linear low density polyethylene LLDPE 7042;

reinforcing fibers: glass fibers, basalt fibers, quartz fibers;

a compatilizer: HDPE-g-MAH; LLDPE-g-MAH;

low-melting polyethylene resin: LLDPE 7042, melting point 120 ℃; EVA 2803, melting point 74 ℃;

initiator: di-tert-butyl peroxide, 2, 5-di-tert-butyl peroxy-2, 5-dimethylhexane, ditert-amyl peroxide.

The relevant performance test criteria or methods are as follows:

bending strength: testing according to ISO 178-2019;

-40 degree notched impact strength: testing according to ISO 180-; testing the temperature to 40 ℃;

heat distortion temperature: ISO75-2-2013 test, test condition 1.82 MPa;

performance retention rate: testing conditions of 120-degree pulverization for 2000h, and observing performance retention rate.

[ PRODUCTION OF REINFORCING FIBER MASTER BATCH ]

According to the proportion shown in the table 1, the polyethylene resin and the compatilizer are mixed and added into a main feeding system of an extruder, meanwhile, the reinforced fiber is added into a side feeding system, and all the components are mixed, extruded and granulated through the extruder to prepare the reinforced fiber master batch.

The reinforced fiber can enter the screw through different areas, and the shearing degree of the reinforced fiber is controlled by adjusting the residence time of the reinforced fiber in the extruder, so that the retention length of the reinforced fiber is controlled.

TABLE 1 proportion (by weight) of each component in the reinforcing fiber master batch

[ preparation of initiator Master batch ]

According to the mixture ratio shown in the table 2, the polyolefin resin and the initiator are added into a main feeding system of an extruder, and are mixed, extruded and granulated to prepare initiator master batches.

TABLE 2 initiator mother particles in the ratio (parts by weight)

Examples 1-7 comparative examples 1-4:

blending the reinforced fiber master batch and the initiator master batch according to the mixture ratio in the table 3 to obtain the polyolefin material. The results of the performance tests are shown in table 4.

TABLE 3 polyethylene materials of examples and comparative examples the respective component ratios (parts by weight)

Table 4: results of Performance testing

As shown in comparative example 1, in comparison with example 2, in comparative example 1, the polyolefin material prepared without adding the initiator masterbatch has poor strength and heat resistance. Comparative example 2 the initiator masterbatch is added with the high melting point polyethylene resin, and in the process of preparing the masterbatch, the initiator is crosslinked with the high melting point polyethylene resin, so that the performance effect is obviously inferior to that of example 2. Comparative example 3 in which the initiator was added directly, the material had large fluctuations in properties due to the easy delamination of the initiator.

The embodiment shows that the strength and short-term heat resistance of the material can be obviously improved by blending the reinforced fiber master batch and the initiator master batch, and meanwhile, the long-term heat resistance of the material can be improved, so that the material has the advantages of high-priority and high-heat resistance.