JPS581737A - Modified polyolefin composition - Google Patents

Abstract

PURPOSE:To improve adhesiveness, impact strength, coatability, etc. of a polyolefin, by blending a modified polymer with a polyolefin, said polymer being obtd. by reacting part of the acidic groups of an acidic group-contg. polymer with other functional group-contg. monomer. CONSTITUTION:A polymer is prepd. from an acid monomer such as acrylic acid, or a copolymer is prepd. from 3-99.9wt% acid monomer, 97-0.1wt% monomer selected from styrene, a (meth)acrylate ester, (meth)acrylamide and (meth) acrylonitrile and 0-50wt% other copolymerizable monomer. Then this (co)polymer is reacted with a monomer having a functional group capable of undergoing an addition or a condensation reaction with a functional groups contained in the polymer to prepare a modified polymer. 0.05-50pts.wt. said polymer is mixed with 99.5-50pts.wt. polyolefin to obtain the titled compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a modified polyolefin having excellent adhesiveness, impact strength and paintability.

Polyolefins have many properties such as excellent mechanical, optical and chemical properties, good moldability, low cost, and low specific gravity, so they are used in an extremely wide range of applications.

However, since polyolefin is a non-polar material, it lacks adhesion with paintable inorganic materials, which poses a major obstacle in practical use. In order to improve these drawbacks, carxyl groups were introduced into polyolefins by grafting acid monomers such as acrylic acid and maleic anhydride onto polyolefins using a cross-wire reactor such as an extruder or hot roll. Various methods have been proposed to do so. However, with these methods, the acid mono added in a short time! - It is extremely difficult to carry out a homogeneous graft reaction of polyolefins, resulting in major problems such as odor caused by volatilization of acid monomers, coloring and deterioration of physical properties due to decomposition of polymers, and equipment limitations of crosstalk reactors. However, the content of acid monomers in polyolefins is limited, and as a result, satisfactory paintability and adhesion cannot be obtained.The inventors of the present invention have conducted intensive research to improve the above-mentioned drawbacks, and as a result, polyolefins have been developed. By reacting some of the acidic groups in the M group-containing polymer with other functional group-containing monomers and blending a modified polymer with This finding led to the completion of the present invention.

That is, the present invention comprises (50 to 99.951 parts by weight of Al polyolefin and (
B) Polymerization of il monomer) and/or acid monomer 5
~99.9% by weight, one or more monomers selected from styrene, (meth)acrylic esters, (meth)acrylic amides, and (meth)acrylonitrile n, 1 to 9
7% by weight and other copolymerizable monomers in an amount of 0 to 5011% ([[)] is reacted with a monomer having a functional group capable of addition or condensation reaction with the functional group contained in the cough polymer. [This relates to a modified polyolefin composition obtained from 5 to 50 parts by weight of LO.

The polyolefin of the present invention ((conversion) includes ethylene,
A homopolymer of α-olefins such as propylene, butene, pentene, etc., such as a low density, medium 1! Polyethylene and high-density polyethylene, crystalline polypropylene, propylene/ethylene copolymer, etc. (
The amount of the (conversion) component used is 50 to 99,951 parts (hereinafter simply abbreviated as parts), preferably 70 to 997 parts; if it is less than 50 parts, the heat deformation resistance of the composition will decrease;
If the amount exceeds 9995 parts, the object of the present invention cannot be achieved.

The acid monomer that is a component of the polymerization (EI) and copolymerization [1] of (B) has a cappable unsaturated bond and an acid group, such as acrylic acid, methacrylic acid, (anhydride)- v Leic acid, fumaric acid, itaconic acid, dodecynyl co/·phosphoric anhydride, crotonic acid, maleic acid monoalkyl ester, 7malic acid monoalkyl ester, itaconic acid monoalkyl ester, mono(2-(meth)acryloyloxyethyl) ) acid phosphate, 2-acrylamido-2-methylpropanesulfonic acid, etc.
These can be used alone or in combination.

(Meth)acrylic acid esters are acrylic acid or methacrylic acid esters.

It refers to esters of tacrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylate.
Acrylic acid m-propyl, (meth)acrylic acid 1s
O-Flohir, n-butyl (meth)acrylate, (meth)acrylic I! 1iH)-butyl, tert-butyl (meth)acrylate, @@C-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ucryl (meth)acrylate, stearyl (meth)acrylate, (
2-hydroxyethyl meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ethylene glycol di(meth)acrylate , trimethylolpropane tri(meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.

Examples of (meth)acrylic acid amides include (meth)acrylamide, N7 methylol (meth)acrylamide, butoxymethyl (meth)acrylamide, and the like.

Examples of other copolymerizable monomers include diethyl ruinate, dibutyl maleate, diethyl fumarate, dibutyl fumarate, diethyl itaconate, dibutyl itaconate, vinyltoluene, α-methylstyrene, dimethylstyrene, and vinyl acetate. It will be done.

The polymer of the present invention (m) is one obtained by polymerizing one or more of the above acid monomers.

Also, the amount of acid monomer used in the copolymer (fl) is 3
~999% by weight (hereinafter simply abbreviated as %), preferably 10~999%, and if it is less than 3%, the effects of the present invention will not be achieved.

The amount of one or more monomers selected from styrene, (meth)acrylic acid esters, (meth)acrylic acid amides, and (meth)acrylonitrile is Q, 1 to 97%, preferably substantially different from the polymer. Otherwise, the hardness and chemical resistance of the resulting copolymer tend to decrease.
If it exceeds 7%, the effects of the present invention cannot be achieved.

Examples of monomers having a functional group capable of addition or condensation reaction with the functional group contained in the polymerized red I) or the copolymer ([I) include monomers with a small number of functional groups such as a hydroxyl group, a glycidyl group, an amino group, an incyanate group, etc. A monomer having a single bridge and a polymerizable unsaturated bond, such as a glycidyl group-containing monomer such as glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, allyl glycidyl ether;
Hydroxyl group-containing monomers such as 2-hydroxypropyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are particularly preferred. The reaction with a functional group such as a glycidyl group or a hydroxyl group is easily carried out in a temperature range from room temperature to 600° C. without a catalyst or using a known catalyst. As a result, a polymer (1) or a copolymer (a polymerizable unsaturated group derived from a monomer having a functional group at ω is introduced. - The usage ratio of polymer I11 or copolymer (
II) Preferably 11 to 50 parts, more preferably 0.5 to 25 parts of the hexamer having a functional group per 100 parts. Substantially the functional group 1 of polymer α) or copolymer vermilion ω
Functional group [LO
It is optimal to use O5 to α5 equivalents, more preferably aQ1 to 13 equivalents.

The amount of the modified polymer (B) used in the present invention is 0.05 to 50 parts, preferably α5 to 30 parts, based on 50 to 9995 parts of the polyolefin. If the amount is not achieved and the amount exceeds 50 parts, the heat deformation resistance of the resulting composition decreases. (B) Any known method can be used to obtain the polymer of component (B), but after combining the solutions, a monomer having a functional group may be reacted to remove the solvent, or after suspension polymerization, the functional group may be removed. The simplest method is to react and separate the 7-year-old honeysuckle to collect the resulting iris metal, so this method is particularly recommended.

In carrying out such polymerization, an initiator such as an azo compound such as azobisisobutylnitrile or a peroxide such as benzoyl peroxide may be used, and if necessary, a known and commonly used molecular weight regulator may be used. You can also use

In the present invention, in addition to the above-mentioned essential substances, various commonly used additives and fillers can be used in combination. For example, as a radical generator, an azo compound such as azobisisobutyronitrile, benzoyl peroxide, tIrt-butylperoxybenzoate, 1,5-bis(1ert-butylbaroxyisopropyl)benzene, 2 , 2-bis(t@rt-butylperoxy)butane, 1.1-bis(t@rt-butylperoxy)-5,3,5-trimethylcyclohexene, 2.5-
Dimethyl-2,5-di(t・rt-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t@rt
-butylperoxy)hexyne-3 and other peroxides.

As a cross-linking aid, triallyl cyanurate, triallyl isocyanurate, diallyl 7-thale), )+7 methylolpropane tri(meth)acrylate, polyalkylene glycol di(meth)acrylate, divinylbenzene, glycidyl(meth)acrylate and (meth)acrylate, ) Esters of acrylic acid, maleic acid and (meth)acrylic acid 2-
Examples include half esters of hydroxyethyl. The amount of this crosslinking aid used is (L2~
20 parts is appropriate.

In addition, examples of crosslinking accelerators include various polyamines and their derivatives, ammonium salts or alkali metal salts of organic carboxylic acids, metal oxides, etc. Specifically, triethylenetetramine, hexamethylenetetramine, hexamethylenediamine carbamate, Ammonium benzoate, sodium stearate, potassium stearate, zinc oxide, magnesium oxide, zinc dioxide, etc. can be mentioned. The amount used is a1 to 5 per part of the radical generator.
0 parts is appropriate.

It is also possible to add amine-based, phenol-based, sulfide-based, phenylalkane-based, phosphite-based, and other antioxidants to control or stop the crosslinking.

Furthermore, it is a must! Depending on the situation, conventional rubber or plastic compounding agents such as fillers, oils, plasticizers, lubricants, colorants, stabilizers, ultraviolet absorbers, etc. can be added.

By blending the prescribed amounts of the above starting materials, zuxinchlor,
The composition of the present invention can be obtained by heating and kneading it in a mixing device such as a Banbury mixer, a Nigoo, or an extruder. The temperature and time of crosstalk are appropriately selected depending on the capacity of the equipment used, the type of resin, etc., but at approximately 100 to 350℃
~20 minutes is appropriate.

The present invention will be explained below according to examples.

Production example (Production of copolymerization medium) 1000 parts of butanol and 10 parts of di-t@rt-butyl peroxide were charged into a reactor equipped with a thermometer, a stirring device, and a reflux cooling device, and heated to 120°C. A liquid mixture consisting of 500 parts of Shun, 500 parts of methyl acrylate, and 30 parts of azobisisobutyronitrile was added dropwise over 6 hours. After keeping the temperature at 120°C for an additional 6 hours, 3 parts of hydroquinone, 5 parts of triadylamine α, and 1 part of glycidyl methacrylate were added, and after keeping the temperature at 120°C for an additional 6 hours, the solvent was distilled under a reduced pressure of 1 mHjl at 200°C. Copolymer B-1 was obtained by removing the solvent until it no longer came out.Into the same reactor as above, 1000 parts of butyl acetate was added to the copolymer B-1.
104 parts of rt-butyl peroxide was heated to 120°C, and 500 parts of styrene, 350 parts of butyl methacrylate,
anhydrous! A liquid mixture consisting of 150 parts of leic acid and 30 parts of azobisisobutyronitrile was added dropwise over 6 hours. After keeping the temperature at 120°C for an additional 6 hours, 3 parts of hydroquinone and 50 parts of 2-hydroxyethyl methacrylate were added, and an additional 2 parts of
After keeping at 120℃ for an hour, 1101Hj+ at 200℃
Copolymer B-2 was obtained by removing the solvent under reduced pressure until no more solvent distilled out, but it was completely identical to copolymer B-1 except that the steps of adding and reacting hydroquinone, triethylamine, and glycidyl methacrylate were omitted. Copolymer c-2 was obtained in the same manner as copolymer B-2 except that the step of adding and reacting copolymer e-1 with hydroquino/and 2-hydroxyethyl methacrylate was omitted. Ta.

Example Table 1: After mixing the indicated raw materials in a Henschel mixer for about 2 minutes, the barrel temperature was 150 to 170°C and the die temperature was 1.
5Or, p6m using a 30mm extruder adjusted to 80℃
It was kneaded and made into pellets. The measured temperature of the contents of the extruder was approximately 200°C. Table 1 shows the results of the adhesion to the steel plate and the impact strength of the obtained pellets of Examples 1 to 4 and Comparative Examples 1 to 2, polypropylene as Comparative Example 6, and high density polyethylene as Comparative Example 4.

<Adhesion to steel plate (180° peel test)> Obtained by melt-bonding the pellets on each side to a thickness of 11wI and then rapidly cooling the α1-thick steel plate degreased with trichlorethylene using a hot press molding machine. After leaving the sheet in a room at 25℃ and 65% relative humidity for 24 hours, the sheet was made into 25m1! A test piece was prepared by cutting. For each test piece (Bot 1 at a speed of 2001!11/min using an Instron type tensile tester)
A 180° peel test was conducted by peeling off the steel plate from the marker using Method 1.

Claims (1)

[Scope of Claims] (A) 50 to 9995 parts by weight of polyolefin and (1
Heavy metal body (1) of 111 monomer and/or m# monomer 3 to 999% by weight, (1) styrene, (meth)acrylic acid esters, (meth)acrylic acid amides, (meth)
One or more monomers α1 selected from acrylonitrile
-97 weight weight 1) Other copolymerizable monomers 0-5
Modified tumor mass Q, 05 to 5 obtained by reacting the copolymer obtained from 0 weight polymer with a monomer having a functional group capable of addition or condensation reaction with the functional group contained in the wrinkled polymer.
A modified polyolefin composition comprising: o.