CN1039818A - Composite polyolefine material and preparation method thereof - Google Patents

Abstract

The invention relates to polyolefinic blended compound material and preparation method thereof, particularly about polyolefine and chlorinatedpolyolefins in the presence of an amount of stablizer.Contain or do not contain matrix material and preparation method that weighting agent makes through melt blending.

Description

Composite polyolefine material and preparation method thereof

The invention relates to polyolefinic blended compound material and preparation method thereof, particularly about intermingling material of polyolefine and chlorinatedpolyolefins and preparation method thereof.

It is well-known to polyolefinic modification before this locust is made, as increase its physical strength, improve cementability, environmental stress crack resistance, thermotolerance, oil-proofness, gasproof body perviousness, flame retardant resistance, printing, dyeability, dimensional stability, reduce molding shrinkage etc.Present composite polyolefine material is according to different service requirementss basically, adopts diverse ways, and polyolefinic some performance is improved.For example polyolefine (as PP, PE) and thermoplastic elastic body blend can be improved (day disclosure special permission: 212443/1985 of toughness and environmental stress crack resistance; 212452/1985; 184547/1985; 131043/1987; US3914342/1974; DE1195489/1964); Elastomer-modified, the Inorganic Fillers Filled polyolefine makes (day disclosure special permission: 166339/1985 that is improved of its thermotolerance, rigidity simultaneously again improving flexible; 133039/1985; 176545/1987); With polypropylene and polypropene blended cementability, oil-proofness, resistance to air loss and the fillable (Japanese Patent: 36421/1970 that makes of chlorosulphonation; 4822/1974; 7334/1974; 15467/1975; 49029/1974 and day disclosure special permission 110754/1977) or the like.As can be seen, polyolefinic modification had been obtained good effect at some aspect of performance in the past, but insufficient is that polyolefinic a certain item or several performances are improved, and fails to make its performance to obtain synthetically, comprehensively improve, and this makes its application be subjected to certain restriction.

The purpose of this invention is to provide a kind of composite polyolefine material and preparation method thereof with excellent comprehensive performance.Composite polyolefine material provided by the present invention is to be that the chlorinatedpolyolefins of 15-55% and this chlorinatedpolyolefins and weighting agent get through melt blending by polyolefine and chlorinity.Wherein polyolefine is the homopolymer or the multipolymer of 2-3 carbon atom alkene, and wherein polyethylene comprises HD PE, LDPE and LLDPE.Its consumption is the 40-95 weight part.Chlorinatedpolyolefins is chlorinatedpolyethylene, Chlorinated Polypropylene III or chlorination polyhutadiene, and its consumption is the 5-60 weight part.Weighting agent can be selected from one or more in lime carbonate, talcum powder, mica powder, kaolin, silicon-dioxide, titanium dioxide, mud, wollastonite, aluminium hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, antimonous oxide, iron powder, aluminium powder, the copper powder.According to the difference of processing conditions, before chlorinatedpolyolefins melting altogether, need its stabilization; Used stablizer is one or both in (I) lead sulfate tribasic, dibasic lead phosphite, lead stearate, calcium stearate, the epoxy soybean oil, consumption is 0.1-10 weight part and (II) CA stablizer (1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane), antioxidant 1010 (four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester), in the magnesium oxide, organic tin (as dibutyl tin laurate) stablizer one or both, consumption is the 0.1-10 weight part.

Method of the present invention at first adds an amount of stablizer in chlorinatedpolyolefins, and its thorough mixing is made the stabilization chlorinatedpolyolefins.Then with polyolefine and stabilization polyolefine at 110-23 ℃ of following melting blending; Wherein contain or do not contain 5-150(weight) part above-mentioned weighting agent.And, just make composite polyolefine material particle of the present invention, and be used for various forming methods as required to be processed into various goods through granulation.

Chlorinatedpolyolefins of the present invention is the chloride thermoplastic elastomer with saturated carbon chains that is obtained through chlorination by polyolefine, compare with other rubber or elastomerics, have good weathering resistance, anti-smelly property, heat-resistant aging, flame retardant resistance, drug-resistant and oil-proofness.

Chlorinatedpolyolefins and polyolefine mix under the degree in the blend of being adopted has close melt viscosity, when blend, can form the successive elastic net structure that runs through mutually with the polyolefin substrate resin, this reticulated structure (1) growth of spherocrystal in the limiting crystal polyolefine effectively, reduce crystalline stress, stablize spherocrystal, increase the intergranular contact, stop crack growth; (2) absorb energy and dispersive stress; (3) cause crazing and shear zone effectively.Therefore, polyolefinic toughness and environmental stress crack resistance are greatly improved.Because the existence of chlorine atom is emitted hydrogenchloride and is covered frosting in the chlorinatedpolyolefins structure during burning, stop the carrying out of combustion reactions, add a small amount of auxiliary flame retardant certainly and can obtain better flame retardant effect.

Because chlorinatedpolyolefins is polar polymer, and can significantly improve polyolefinic cementability, printing, dyeability, electrodepositable and oil-proofness behind the polyolefin blend.This chlorinatedpolyolefins is the unformed or micro-crystallization thermoplastic elastomer of polarity, mineral filler there is very strong covering property, behind it and polyolefin blend, do not just win high its toughness, and the dispersiveness of filler in resin significantly improved, thereby can strengthen loading level, so not only reduce this one-tenth, but also improved thermotolerance, the dimensional stability of material.Rigidity and resistance to air loss.

Illustrate the present invention with concrete example below, the wherein said consumption that reaches is parts by weight, and these examples just illustrate further the present invention, are not limiting the scope of the invention.

Embodiment 1

Sym-propene polymer resin PP1300 67.5 weight parts, stabilization chlorinatedpolyethylene CPE-3614 32.5 weight parts or PP1300 67.5 weight parts, stabilization chlorinatedpolyethylene CPE-3614 32.5 weight parts, 50 parts of talcum powder, at 170-190 ℃ of following melt blending, then this blend is made 3-5mm sheet material, and make standard test specimen by respective standard, according to standard method, carry out various performance tests, the results are shown in table 1, provide the test result of pure PP1300 sample in the table 1 simultaneously.

Table 1

Test number (weight part) No. 1 No. 2 No. 3

The PP1300(weight part) 100 67.5 67.5

The CPE(weight part) 0 32.5 32.5

Shock strength kgcm/cm GB1043-79 5.45 51.38 18.30

Rate mm/min GB2408-80 28.5 21.4 18.0 is prolonged in burning

Ball indentation hardness kg/cm HG2168-65 6.71 5.00 6.81

Thermal expansivity 10.5 * 10 ^-56.5 * 10 ^-54.5 * 10 ^-5

Surface energy dn/cm＞38＞38

(+50 parts of talcum powder)

Embodiment 2

Homemade high density polyethylene 5000S, 80 weight parts, stabilization chlorinatedpolyethylene CPE-3614,20 weight parts, 10 parts of antimonous oxides, at 130-165 ℃ of melt blending, be made into the sheet material of 1-4mm then, be processed into standard test specimen and survey its environmental stress crack resistance, flame retardant resistance, surface hardness or above-mentioned blend is made standard impact specimen with injector survey its shock strength after granulation the results are shown in table 2, and the respective performances index that provides pure HDPE in table 2 simultaneously is so that comparison.

Table 2

Test number 4# 5#

HDPE weight part 100 80

CPE weight part 0 20

ESCR tests F50hr 24 424

Shock strength kgcm/cm 22 100

Rate of combustion mm/min 20.0-

Incendivity is flammable from putting out

The ball impression is more spent kg/cm 2.0 1.6

(10 parts of+SbO)

Embodiment 3

High density polyethylene 5000S, 80 weight parts, stabilization chlorinatedpolyethylene CPE-3614,20 weight parts, 50 parts of mica powders, blend granulation after 130-165 ℃ of fusion.Then this pellet is broken into standard test specimen on injector and survey its shock strength, surface hardness.This is made the sealing bucket that wall thickness is 0.5-2mm, and the gasoline of packing into is surveyed its gasproof body or flux perviousness, the results are shown in table 3.

Table 3

Test number 6#

HDPE weight part 80

CPE weight part 20

Test number 6#

Mica powder weight part 50

Shock strength kgcm/cm GB1043-79 32

Ball indentation hardness kg/cm HG2-168-65 3.5

Resistance to air loss dress gasoline was observed ne-leakage after 15 days

Claims (7)

1, composite polyolefine material, wherein contain:

(1) homopolymer of 2-3 carbon atom alkene or multipolymer;

(2) chlorinatedpolyolefins of 2-4 carbon atom;

(3) stablizer: (I) three salt one or both in lead sulfate, dibasic lead phosphite, lead stearate, phosphatidic acid calcium, epoxy soybean oil; (II) the CA stablizer (1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane), one or both in antioxidant 1010, (four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] quaternary amyl alcohol ester), magnesium oxide, the organic tin (as dibutyl tin laurate).

2, according to the matrix material of claim 1, wherein also has weighting agent.

3, according to the matrix material of claim 1 or 2, it is characterized in that chlorinatedpolyolefins is a chlorinatedpolyethylene, content is 15-55%.

4, according to the matrix material of claim 1 or 2, wherein the consumption of polyolefine and chlorinatedpolyolefins is respectively 40-95 weight part and 5-60 weight part.

5, according to the matrix material of claim 1 or 2, wherein the consumption of stablizer is 0.1-10 weight part stablizer (I) and 0.1-10 weight part stablizer (II).

6, according to the matrix material of claim 2, wherein weighting agent is one or more in lime carbonate, talcum powder, mica powder, Gao Ling, silicon-dioxide, titanium dioxide, red mud, wollastonite, aluminium hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, antimonous oxide, iron powder, aluminium powder, the copper powder, and consumption is 5-150 part.

7, a kind of method for preparing the described matrix material of above-mentioned arbitrary claim is characterized in that:

(1) 5-60 weight part chlorinatedpolyolefins is mixed with 0.1-10 part stablizer (I) and 0.1-10 part stablizer (II);

(2) then with 40-95 weight part polyolefine 110-230 ℃ of melting mixing, wherein contain or do not contain 5-150 part weighting agent.

(3) then carry out granulation and be used for various forming methods.