JPH0586141A - Production of thermoplastic resin excellent in liquid repellency - Google Patents

Abstract

PURPOSE:To obtain the title resin excellent in liquid repellency and its retention by subjecting a specified unsaturated copolymer resin and a specified amount of a polyfluoroalkylated (meth)acrylate to radical polymerization conditions to produce a grafted copolymer. CONSTITUTION:100 pts.wt. unsaturated copolymer resin comprising 80-99.95mol% at least one 2-12C alpha-olefin (e.g. propylene) and 0.05-20mol% cycloolefin of the formula (wherein R<1> is 2-5C alkylidene or alkenyl; R<2> is a 1-5C hydrocarbon group; and n is 0-2) and 0.5-90 pts.wt. polyfluoroalkylated (meth)acrylate (e.g. perfluorooctylethyl methacrylate) or both this compound and a vinylidene monomer (e.g. styrene) are subjected to radical polymerization conditions to produce a grafted copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermoplastic resin having an excellent liquid repellency, which comprises an olefin copolymer grafted with a polyfluoroalkyl group-containing (meth) acrylic acid ester. This resin can be extrusion-molded and injection-molded and is useful for a laminated resin container such as a container for motor oil and chemicals, and an inner layer film for a laminated film.

[0002]

2. Description of the Related Art Liquid repellents composed of a polymer containing a polyfluoroalkyl group or a copolymer of a monomer containing a polyfluoroalkyl group and another monomer have been conventionally known. (JP-A-58-59277, etc.), a method for producing a liquid-repellent molded article by melting and kneading such a liquid-repellent agent with an olefin resin has also been proposed (JP-A-3-7).
745).

However, although the resins obtained by these methods are excellent in liquid repellency, they are not always satisfactory in that they retain liquid repellency for a long time with respect to solvents such as acetone and methyl ethyl ketone. It was As other means for making the surface of the resin lyophobic, (i) coating the surface of the molded article with a compound having a low surface tension, (ii) plasma treatment of the compound having a low surface tension on the surface of the molded article, etc. There is a method such as graft addition using the method described in (1), but these are somewhat complicated because the molded product is further processed. Further, regarding (i), the liquid repellent layer is rubbed. Therefore, there are drawbacks such that it is easily peeled off and the liquid repellency is lowered in a short time, and regarding (ii), a special machine is required.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an olefin resin which is capable of extrusion molding and injection molding and exhibits excellent liquid repellency for a long time even in a solvent such as acetone or methyl ethyl ketone. It is a thing.

[0005]

The present invention has 2 to 1 carbon atoms.
At least one α-olefin of 80 to 99.95
Mol% and the following general formula (I)

[0006]

[Chemical 2]

(Wherein R ¹ is an alkylidene group or alkenyl group having 2 to 5 carbon atoms; R ² is a hydrocarbon group having 1 to 5 carbon atoms; n is an integer of 0, 1 or 2). The unsaturated copolymer resin composed of 0.05 to 20 mol% of the cyclic olefin shown is a polyfluoroalkyl group-containing (meth) acrylic acid ester, or a polyfluoroalkyl group-containing (meth) acrylic acid ester and vinyl or vinylidene. The present invention provides a method for producing a thermoplastic resin, which comprises producing a graft-modified copolymer by subjecting the monomer to radical polymerization conditions.

Graft-Modified Copolymer The graft-modified copolymer comprises at least one α-olefin (i) having 2 to 12 carbon atoms and at least one cyclic olefin (ii) represented by the above general formula (I). The unsaturated copolymer resin (a) comprising a polyfluoroalkyl group-containing (meth) acrylic acid ester (b) or a polyfluoroalkyl group-containing (meth) acrylic acid ester and a vinyl or vinylidene monomer (b) ) Together with radical polymerization conditions.

(I) α-Olefin As the α-olefin having 2 to 12 carbon atoms which is a raw material for producing the unsaturated copolymer resin (a), ethylene,
Propylene, butene-1, pentene-1, hexene-
1, octene-1,3-methyl-butene 1,3-methyl-pentene-1,4-methyl-pentene-1,3,3-
Dimethyl-butene-1,4,4-dimethyl-pentene-
1,3-methylhexene-1,4-methyl-hexene-
1,4,4-dimethyl-hexene-1,5-methyl-hexene-1, allylcyclopentane, allylcyclohexane, styrene, allylbenzene, 3-cyclohexylbutene-1, vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, 2-vinylbicyclo [2,2,1] -heptane and the like can be mentioned.
Among these, preferable examples are ethylene, propylene, butene-1, 3-methyl-butene-1, 4-methyl-pentene-1, styrene and the like, and particularly preferable examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

(Ii) Cyclic Olefin The other raw material for producing the unsaturated copolymer resin is a cyclic olefin represented by the following formula (I):

[0011]

[Chemical 3]

(Where R is¹Is an alkylide having 2 to 5 carbon atoms
Group or alkenyl group; R²Is carbonized water having 1 to 5 carbon atoms
A basic group; n is an integer of 0, 1 or 2)
It is a compound. R¹Alky having 2 to 5 carbon atoms represented by
As a lidene group, ═CH (CH₃), = CH (C
H₂) CH₃, = CH (CH₂)₂CH₃, = C (CH
₃)₂, = C (CH₃) (CH₂CH₃), = C (CH
₂CH₃)₂And an alkenyl group having 2 to 5 carbon atoms
Then, -CH = CH₂, -CH₂-CH = CH₂,-
CH ₂-C (CH₃) = CH₂, -CH₂-CH = CH
(CH₃), -CH₂-CH = C (CH₃)₂, -CH
₂-CH₂-C (CH₃) = CH₂, -CH₂-CH ₂
-CH = CH (CH₃) Etc. can be mentioned. n is
It is an integer up to 2, but 0 or 1 is preferred. concrete
Examples thereof include the compounds listed in Table 1.
These cyclic dienes may be used alone or in combination of two or more.
You may use.

[0013]

[Table 1]

(A) Unsaturated Copolymer Resin The above α-olefins (i) and cyclic olefins (ii)
And using the known Kaminsky catalyst and the known method and apparatus similar to those for the α-olefin polymer.
Alternatively, an unsaturated copolymer resin can be produced by random copolymerization. Specifically, the Periodic Table IVB
It can be produced by copolymerization with a catalyst composed of a transition metal compound selected from the group consisting of a group and aluminoxane.

The transition metal compounds selected from the group consisting of Group IVB of the periodic table include ethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride and ethylenebis (4
Examples include 5,6,7-tetrahydro-1-indenyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) titanium dichloride and the like. Aluminoxanes are represented by the following general formula (II)

[0016]

[Chemical 4]

An organoaluminum compound represented by: In this general formula, R is an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc., particularly preferably a methyl group, and n is 2
As described above, it is preferably an integer of 4 or more and 100 or less.

As a polymerization method, specifically, a hydrocarbon solvent such as hexane, heptane, benzene, and toluene can be used to carry out the polymerization by a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method. The unsaturated copolymer resin used in the present invention has a cyclic olefin content of 0.05 to 20 mol%, preferably 0.1 to 10 mol%.
If it is less than 0.05 mol%, there is a drawback that it is difficult to increase a desired graft ratio because the unsaturated copolymer resin has a small amount of unsaturated groups. On the other hand, if it exceeds 10 mol%, the copolymerization rate will be slow in the production of the unsaturated copolymer resin, and in the case of slurry polymerization, the solvent-soluble by-product polymer will increase and the viscosity of the polymerization system will increase, resulting in poor productivity. However, there are drawbacks such that the resulting unsaturated copolymer becomes sticky and the resinous state is not maintained.

The molecular weight of the unsaturated copolymer resin is not particularly limited as long as it maintains the above-mentioned resin state. For example, when the α-olefin is mainly propylene, JIS-
The melt flow rate (MFR) measured according to K-6758 is usually 0.001 to 3000 g / 10 min,
A molecular weight corresponding to 0.01 to 2,000 g / 10 minutes, particularly preferably 0.05 to 1000 g / 10 minutes is preferable. Further, this unsaturated copolymer resin has an elastic modulus of 500 to 5 according to JIS-K-7203.
It is preferably 10,000 kg / cm ² . For example, α-
When the olefin is mainly composed of propylene, the elastic modulus is preferably 1,000 to 20,000 kg / cm ² .

Examples of the unsaturated copolymer resin (a) include the cyclic olefins and various combinations of block copolymers and random copolymers selected from the above α-olefins. Among them, the following are preferable. Propylene-5-vinylcyclohexane [2,2,1] hept-2-ene random copolymers, propylene-ethylene-8-ethylidene tetracyclododecene [4,4,0,1 ^{2, 5,} 1 ^7,10] -3 -Dodecene random copolymer, propylene-butene-1.5-vinylcyclo [2,2,1] hept-2-ene random copolymer, propylene-8-ethylidenetetracyclo [4,4]
4,0,1 ^2,5, 1 ^7,10] -3-dodecene random copolymers, propylene-5-vinylcyclohexane [2,2,1] hept-2-ene block copolymers.

(B) Polyfluoroalkyl group-containing (me
Examples of the (meth) acrylic acid ester containing a polyfluoroalkyl group used as a graft monomer in the acrylic acid ester graft modified copolymer include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOC (CH ₃ ) =
_{CH 2 CF 3 (CF 3)} CF (CF 2) 6 CH 2 CH 2 OCO
_{CH = CH 2 CF 3 (CF} 3) CF (CF 2) 6 CH 2 CH 2 OCO
_{C (CH 3) = CH 2} CF 3 (CF 2) 6 CH 2 CH 2 OCOCH = CH 2 CF 3 (CF 2) 6 CH 2 CH 2 OCOC (CH 3) =
_{CH 2 CF 3 (CF 2)} 4 CH 2 CH 2 OCOCH = CH 2 CF 3 (CF 2) 4 CH 2 CH 2 OCOC (CH 3) =
_{CH 2 CF 3 (CF 2)} 7 OCOCH = CH 2 CF 3 (CF 2) 7 OCOC (CH 3) = CH 2 and the like.

Vinyl or Vinylidene Monomers Also, as the vinyl or vinylidene monomers which are optionally used together with the above-mentioned esters as graft monomers, for example, styrenic monomers such as styrene, nucleus-substituted styrenes such as Methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, chlorostyrene, α-substituted styrene such as α-methyl styrene, α-ethyl styrene, acrylic acid ester (especially C ₁ -C ₇ alkyl ester), methacrylic acid ester (especially , C ₁ -C ₇ alkyl ester), vinyl halide or vinylidene (particularly vinyl chloride, vinylidene chloride), acrylonitrile, methacrylonitrile,
Vinylnaphthalene, vinylcarbazole, acrylamide, methacrylamide and the like can be used, and these can be used alone or as a mixture.

Production of Graft-Modified Copolymer The graft-modified copolymer is produced by subjecting the unsaturated copolymer resin (a) together with the monomer (b) to a conventionally known radical graft polymerization condition. You can For example, in the coexistence of the unsaturated copolymer resin and the monomer, γ-ray, a method of irradiating with radiation such as an electron beam, a method of irradiating the unsaturated copolymer resin with radiation and then allowing the monomer to coexist, Any method such as coexistence of an unsaturated copolymer resin and a monomer in a solution state, a molten state or a dispersed state, and graft polymerization in the presence or absence of a radical polymerization catalyst can be adopted in the present invention. Of these, the method of performing graft polymerization in a solution or molten state is preferable.

Radical polymerization catalysts include benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, t-butyl hydroperoxide, t-butyl peroxyacetate, diisopropyl peroxydicarbonate and 2,2-bis. Organic and inorganic peroxides such as (t-butylperoxy) octane, methyl ethyl ketone peroxide, potassium peroxide and hydrogen peroxide, and azo compounds such as α, α′-azobisisobutyronitrile. The peroxide can be used as a redox system in combination with a reducing agent. For example, there is a combination of hydrogen peroxide and a ferrous salt.

These radical polymerization catalysts are appropriately selected in relation to the type of monomer and the polymerization method, and one kind or two or more kinds may be used in combination. The temperature of the radical graft polymerization reaction is usually 30 ° C to 350 ° C, preferably 50 ° C.
C. to 300.degree. C., and the polymerization time is 30 seconds to 50.
The time is preferably in the range of 1 minute to 24 hours.

The amount of the radical polymerization catalyst used is appropriately selected from the range of 0 to 100 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the unsaturated copolymer resin. When it is necessary to adjust the molecular weight of the polymerized portion of the monomer, a molecular weight adjusting method that is usually used in radical polymerization can be used. For example, the object can be achieved by the polymerization temperature, the amount of radical polymerization catalyst added, the amount of monomer used, the addition of a molecular weight modifier such as mercaptans and 2,4-diphenyl-4-methyl-1-pentene. it can.

The copolymerization ratio between the polyfluoroalkyl group-containing (meth) acrylic acid ester and the vinyl or vinylidene monomer in the graft-modified copolymer decreases as the ratio of the polyfluoroalkyl group-containing (meth) acrylic acid ester decreases. , The liquid repellency decreases, so the weight ratio is 1: 0 to 1: 9
Is preferred. Further, based on 100 parts by weight of the unsaturated copolymer,
The polyfluoroalkyl group-containing (meth) acrylic acid ester is mixed in an amount of 0.5 to 90 parts by weight, preferably 1 to 50 parts by weight. When the blending ratio of the polyfluoroalkyl group-containing (meth) acrylic acid ester decreases, the liquid repellency decreases. On the other hand, if the amount is too large, the extrusion-moldability and injection-moldability of the graft-modified olefin-based copolymer deteriorate.

Incidentally, the graft copolymerization is generally equivalent to polymerizing a monomer which should give a "branch" polymer in the presence of the "stem" polymer, and thus, an ideal backbone-branched structure polymer is obtained. In addition to coalescence, it is often observed that a polymer of this monomer itself that does not "branch" is by-produced. Therefore, also in the present invention, the "graft-modified copolymer" includes a mixture containing such a by-product.

The polyfluoroalkyl group-containing (meth) acrylic acid ester-grafted olefin-based copolymer of the present invention is melt-kneaded, extruded in a strand shape, and cut for extrusion molding, injection molding, compression molding. Can be pellets. Examples of the melt kneading include a heating roll and an extruder. On a small scale, there is Brabender Plastograph.

[0030]

The resin obtained by the practice of the present invention is
It is possible to maintain liquid repellency for a long period of time not only against water and alcohol, but also against acetone, methyl ethyl ketone and the like. The reason for this is that it is possible to firmly fix the polyfluoroalkyl group-containing (meth) acrylic acid ester (co) polymer part, which is the part that exhibits liquid repellency, to the unsaturated copolymer by a graft reaction. It is thought to be because of this.

[0031]

EXAMPLES Next, the present invention will be described in more detail by way of examples. <Example 1> In a separable flask, propylene and 5 were added.
-A random copolymer with vinylcyclo [2,2,1] hept-2-ene {content of 5-vinylcyclo [2,2,1] hept-2-ene is 2.4 mol%} 100 parts by weight,
15 parts by weight of perfluorooctylethylmethacrylate, 15 parts by weight of styrene, 2 parts by weight of t-butylperoxybenzoate, and 1000 parts by weight of toluene were supplied, and 1
The reaction was carried out at 20 ° C. for 6 hours.

The reaction product obtained was poured into a large amount of cold methanol to precipitate a polymer, which was washed by filtration and then dried under reduced pressure to obtain a graft-modified copolymer. This graft-modified copolymer was melt-kneaded for 5 minutes at 230 ° C. and 60 rpm using a Brabender Plastograph to obtain a resin composition. This was pressed at 190 ° C. and a pressure of 100 kg / cm ^{2 for} 5 minutes to form a sheet of 100 × 100 × 1 mm.

Example 2 As an unsaturated copolymer resin,
Propylene and 8-ethylidene tetracyclo [4,4,4]
Copolymer with (0,1 ^{2,5,1 7,10} ] -3-dodecene (8
- ethylidene tetracyclododecene [4,4,0,1 ^2,5, 1
^7,10 ] -3-dodecene content of 2.8 mol%) was used to carry out the graft reaction in the same manner as in Example 1,
Subsequently, a sheet was produced.

Example 3 Polymerization was performed in the same manner as in Example 1 except that methyl methacrylate was used instead of styrene, and then a sheet was produced.

Comparative Example 1 A propylene homopolymer (MFR 3.5 g / 10 g was used instead of the unsaturated copolymer resin.
Min) was used to carry out a graft reaction in the same manner as in Example 1, and subsequently a sheet was produced.

[Evaluation Test Example] Using the sheets obtained in Examples 1 to 3 and Comparative Example 1, the contact angle was measured with ion-exchanged water. Further, as a sustainability evaluation, the contact angle was measured with ion-exchanged water after immersion in 23 ° C. acetone for 1 to 24 hours and immersion in 79.5 ° C. methyl ethyl ketone for 1 hour. The results are shown in Table 2.

[0037]

[Table 2]

As is clear from the results shown in Table 2, the graft-modified copolymers (Examples 1 to 3) using the unsaturated copolymer as the trunk polymer have a contact angle even after immersion treatment with acetone or the like. The graft-modified copolymer using the propylene homopolymer (Comparative Example 1) as a trunk polymer has a slightly lowered contact angle due to immersion in acetone or the like. It can be seen that the water repellency is considerably reduced.

This is because when the trunk polymer is an unsaturated copolymer resin, the unsaturated portion and the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer portion in the resin are firmly fixed by a graft reaction. Therefore, even if treated with acetone and methyl ethyl ketone, which are good solvents for the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer, the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer is less likely to be released from the sort surface, Therefore, it is considered that the water repellency is less likely to decrease.

On the other hand, when the backbone polymer is a propylene homopolymer, since the propylene homopolymer generally has no unsaturated part, the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer part and the propylene homopolymer are used. Grafting reaction with homopolymer is difficult to occur, and when treated with acetone etc., the polyfluoroalkyl group-containing (meth) acrylic acid ester polymer is easily released from the sheet surface, so the contact angle decreases, that is, water repellency. Is expected to decrease.

Claims (1)

[Claims] 1. An α-olefin having 2 to 12 carbon atoms and at least one type of 80 to 99.95 mol% and the following general formula (I): (Wherein R ¹ is an alkylidene group or alkenyl group having 2 to 5 carbon atoms; R ² is a hydrocarbon group having 1 to 5 carbon atoms; n is an integer of 0, 1 or 2) 100 parts by weight of an unsaturated copolymer resin (a) consisting of 0.05 to 20 mol% of an olefin is used as a polyfluoroalkyl group-containing (meth) acrylate ester or a polyfluoroalkyl group-containing (meth) acrylic acid ester. A method for producing a thermoplastic resin, which comprises producing a graft-modified copolymer by subjecting it to radical polymerization conditions together with 0.5 to 90 parts by weight of a vinyl or vinylidene monomer (b).