JPH0397705A - Production of silane modified low molecular olefin based polymer - Google Patents

Abstract

PURPOSE:To obtain the title polymer having large lubricating properties, free from breed-out phenomenon and having good compatibility when added to a polar resin and suitable as an additive for resin by thermally degrading a polyolefin graft-modified with a silane compound under specific conditions. CONSTITUTION:A polyolefin graft-modified with 0.1-10wt.%, preferably 0.5-7% silane compound (preferably vinyltrimethoxysilane or vinyltriethoxysilane) and having 0.1-200, preferably 1-150 melt flow rate is degraded in an inert gas at 300-450 deg.C, preferably 320-430 deg.C for 0.5-10hr, preferably 1-7hr to provide the aimed polymer having 500-20000, preferably 1000-18000 number-average molecular weight. Double bond in the polymer is preferably 1-10 based on 1000 carbon.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a silane-modified low molecular weight olefin polymer. More specifically, the present invention relates to a method for producing a silane-modified low-molecular-weight olefin polymer useful as an additive for resins.

[Prior Art] Conventionally, low molecular weight olefin polymers such as low molecular weight polyethylene and low molecular weight polypropylene are known as additives for resins.

[Problems to be Solved by the Invention] However, when used as additives for resins, particularly lubricants for resins, conventional products have a drawback of plate-out although they have high lubricity.

[Means for Solving the Problems] The present inventors have developed a low-molecular-weight olefin polymer useful as a resin lubricant that has high lubricity and is extremely unlikely to plate out when added as an additive for resins. As a result of intensive research, the present invention has been achieved.

That is, in the present invention, a polyolefin graft-modified with 0.1 to 10% by weight of a silane compound and having a melt flow rate of 0.1 to 200 (hereinafter abbreviated as silane-modified polyolefin) is treated in an inert gas at 300 to 450°C. This is a method for producing a silane-modified low-molecular-weight olefin polymer having a number average molecular ffi of 500 to 20,000, which is characterized by heat decomposition for 5 to 10 hours.

Examples of the silane compound in the present invention include silane compounds having an olefinically unsaturated bond, such as vinyltrimethylsilane, vinyltriethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane. It will be done.

Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferred.

The polyolefin portion of the silane-modified polyolefin in the present invention is a homopolymer of an α-olefin selected from the group consisting of ethylene, propylene, 1-butene, and 4-methyl-apentene, or a copolymer of two or more of these α-olefins. Examples include polymers and copolymers of one or more of these α-olefins and one or more other α-olefins and/or vinyl compounds. Examples of other α-olefins include olefins having 5 to 18 carbon atoms, such as 1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. Vinyl compounds include unsaturated carboxylic acids or their anhydrides [(meth)acrylic acid, maleic anhydride, etc.] and (
Alkyl meth)acrylate (the alkyl group includes a group selected from the group consisting of methyl, ethyl and butyl), and the like.

The melt flow rate (MFR) of the silane-modified polyolefin in the present invention is usually 0.1 to 200, preferably 1 to 150. If the MFR is less than 0.1, the resulting silane-modified low molecular weight olefin polymer will be non-uniform and heavily colored. When the MFR exceeds 200, the odor of the obtained silane-modified low molecular olefin polymer increases. M
For example, when the polyolefin part is polypropylene, FR is JIS K6758 (temperature 230℃, load 2
．． 16kgf), in the case of polyethylene, JIS K
6760 (temperature 190°C, load 2.16kgf)
It can be measured according to

The silane-modified polyolefin in the present invention is obtained by graft polymerizing a silane compound having an olefinically unsaturated bond to the polyolefin described in the polyolefin section above. Specifically, the silane-modified polyolefin in the present invention can usually be produced by reacting a polyolefin with a silane compound having an olefinic unsaturated bond in an extruder in the presence of a radical generator (for example, a special Kosho 48-1711
Publications, etc.).

The silane compound in the silane-modified polyolefin in the present invention is usually 0.1 to 10% by weight, preferably 0.5 to 7% by weight based on the silane-modified polyolefin.

If the amount of the silane compound is less than 0.1% by weight, the resulting silane-modified low molecular weight olefin polymer will have insufficient lubricity when used as an additive for resins, particularly as a lubricant for resins.

When the resulting silane-modified low molecular weight olefin polymer is used as a lubricant for resins when the amount exceeds 10% by weight, excessive lubrication occurs and the moldability of the resin deteriorates.

The silane-modified low-molecular-weight olefin polymer in the present invention can be obtained by thermally degrading the above-mentioned silane-modified polyolefin in an inert gas, usually at 300 to 450°C for 0.5 to 1'0 hours.

Inert gases include argon, nitrogen, carbon dioxide and water vapor. Nitrogen is preferred. The flow rate is typically 0.1 to 1001/min.

The reaction temperature is 300 to 450°C, preferably 320 to 43°C.
It is 0°C. If the reaction temperature is less than 300'C, the reaction will take a long time (usually 30 hours or more) and the resulting silane-modified low molecular weight olefin polymer will have a poor hue. 450℃
If the amount exceeds 100%, the odor will increase.

The reaction time is 0.5 to 10 hours, preferably 1 to 7 hours. If the reaction time is less than 0.5 hours, the odor of the obtained silane-modified low-molecular-weight olefin polymer will increase, and it will be difficult to obtain a homogeneous polymer. If it exceeds 10 hours, the hue will deteriorate.

The pressure is usually normal pressure to 200 kg/cm2, preferably normal pressure to 150 kg/cm2. If the pressure is less than normal pressure, the color of the obtained silane-modified low molecular olefin polymer will deteriorate, and if it exceeds 200 kg/cm2, the odor will increase.

The heat sterilization method may be either a batch method or a continuous method, but a continuous method is preferred.

As a continuous method, a normal method is also used, as disclosed in Japanese Patent Application No. 1-1978.
It can also be carried out by the method described in Specification No. 74 (hereinafter abbreviated as the above-mentioned patent specification), such as the method using a tubular reactor or the method of adding a phenolic antioxidant and performing thermal degradation. can.

Examples of tubular reactors include those in which two or more tubes with different inner diameters are connected in series, and those that use a static mixer as part or all of the tubular reactor. It can also be used after being immersed. Details are given in the patent specifications mentioned above.

Examples of phenolic antioxidants include 2,6-di-t
ert-butyl-4-methylphenol (B.H.T)
, 2-tert-butyl-4-methylphenol (B
．． H. A) , 6-t, ert-butyl-2,4-methylphenol (24M6B), 2,6-diter
Examples include hindered phenol compounds such as t-butylphenol (26B) and 2-tert-butyl-4-ethylphenol (24M6B), which are described in the above-mentioned patent specifications.

A catalyst can also be used for the purpose of promoting the thermal degradation reaction. As a catalyst, a radical generating catalyst [peroxides such as benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide; 2,2'-
Azonitriles such as azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and 4,4'-azobis(4-cyanovalerianic acid)]. and cranking catalysts (silica alumina, silica magnesia, activated clay, etc.).

The silane-modified low-molecular-weight olefin polymer used in the present invention usually has from 1 to 10, preferably from 2 to 7 double bonds per 1,000 carbon atoms. If the number of double bonds is less than 1, the resulting silane-modified low-molecular-weight olefin polymer will have insufficient compatibility when added to a polar resin, and if it exceeds 10, the heat resistance of the resulting silane-modified low-molecular-weight olefin polymer will decrease. Sexuality decreases. The number of double bonds is determined by nuclear magnetic resonance spectroscopy (NM
R method), etc.

The number average molecular weight of the silane-modified low molecular weight olefin polymer in the present invention is generally 500 to 20,000, preferably 1,000 to 18,000. If the number average molecular weight is less than 500, the resulting silane-modified low-molecular-weight olefin polymer will have increased stickiness and poor heat resistance.

If it exceeds 20,000, the resulting silane-modified low molecular weight olefin polymer will have insufficient lubricity as a lubricant for resins.

The softening point of the silane-modified low molecular weight olefin polymer in the present invention is usually 70 to 200'C, preferably 90 to 180'C.

The melt viscosity of the silane-modified low molecular weight olefin polymer in the present invention at 160°C is usually 30 to 20,000c.
ps, preferably 50 to 15,000 cps.

The silane-modified low molecular weight olefin polymer obtained by the present invention is useful as an additive for resins, particularly as a lubricant for resins.

When used as a lubricant for resins, target resins include vinyl chloride resins, polyolefin resins (polyethylene, polypropylene, etc.), polystyrene resins (polystyrene, AS resins, ABS resins, MBS resins, etc.), and polyester resins (polyethylene terephthalate, polyester resins, etc.). butylene terephthalate, polycarbonate, etc.), polycarbonate resin (6 nylon, 6,6 nylon, 11 nylon,
12 nylon, etc.) and aromatic polyether resins (
polyphenylene ether, etc.).

The amount of the silane-modified low-molecular-weight olefin polymer obtained by the present invention added to the resin is usually 0.1 to 10 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the tree yJ'a.
5 parts by weight.

The silane-modified low-molecular-weight olefin polymer obtained by the present invention can also be used as a shape-processability improver for various resins, a dispersant for pigments and fillers, a surface modifier, and the like. When used for such purposes, the amount of the silane-modified low molecular olefin polymer obtained by the present invention should be 1/1 of the target resin.
The amount is usually 0.05 to 50 parts by weight, preferably 0.1 to 30 parts by weight.

When adding the silane-modified low-molecular-weight olefin polymer obtained by the present invention to a resin, it may be added separately from the resin, or it may be dispersed in the resin in advance at a high concentration (master batch). good.

Furthermore, the silane-modified low-molecular-weight olefin polymer obtained by the present invention can be added to resins together with other resin additives depending on various uses.

Other resin additives include heat stabilizers, antioxidants, ultraviolet absorbers, pigments and fillers, plasticizers, and antistatic agents.

Mixing with the silane-modified low molecular weight olefin polymer resin obtained by the present invention can be carried out using various known mixers. Mixing machines include Henschel mixer, extruder,
Examples include Brabender, Niichi Goo, and Banbury Mixer.

[Examples] The present invention will be further described below with reference to Examples, but the present invention is not limited thereto. Parts in the examples are parts by weight.

Example 1 A silane-modified propylene polymer grafted with 1% by weight of vinyltrimethoxysilane (
Propylene homopolymer, density: O. 91, MFR:
70) 1000g was charged under nitrogen atmosphere.

From then on, nitrogen continued to be vented into the Kolben until the end of thermal degradation. Next, the mixture was heated with a mantle heater to raise the temperature and, without stirring, thermal degradation was carried out at 355°C for 2 hours. Next, the heat-reduced material was cooled to 200° C. and then taken out from the colben. The obtained silane-modified low molecular weight propylene polymer has a number average molecular weight ff
i3,500, melt viscosity at 160°C 150 cps
It was a hard white wax with a softening point of 148°C, 5.3 double bonds per iooo carbon, and grafted with 1% by weight of vinyltrimethoxysilane.

Example 2 Using 1000 g of a silane-modified brobylene polymer (propylene monopolymer, density: 0.91, MFR: 20) grafted with 3% vinyltrimethoxysilane, heat anneal was carried out at 350° C. for 1.5 hours. The same operations as in the example construction were performed except for the following steps. The obtained silane-modified low molecular weight propylene polymer had a number average molecular ffi of 6,000, a melt viscosity at 160°C of 1000 cps, a softening point of 150°C, and a
It was a hard white wanx with 3.2 double bonds per 00 carbons and grafted with 3% by weight vinyltrimethoxysilane.

Example 3 The same procedure as in Example was carried out except that 1000 g of a silane-modified propylene polymer grafted with 3% by weight of vinyltriethoxysilane (propylene homopolymer, density: 0.91, MFR: 70) was used. The obtained silane-modified low molecular weight propylene polymer had a number average molecular weight of 3.80.
Melt viscosity 170 cps at 0.160°C, softening point l
At 49°C, it was a hard white wax with 5.1 double bonds per 1000 carbons and grafted with 3% by weight vinyltriethoxysilane.

Example 4 Silane-modified ethylene polymer (ethylene homopolymer, density:
0.92, MFR: 9.5) Using 1000g,
The same operation as in the example was carried out except that heat sterilization was performed at 375°C for 2 hours. The obtained silane-modified low-molecular-weight ethylene polymer had a number average molecular ffi of 2,100, a melt viscosity at 140°C of 350 cps, a softening point of 107°C, 4.1 double bonds per 1000 carbons, and 1% by weight of vinyl. It was a hard white wax grafted with trimethoxysilane.

Comparative Example 1 The same operation as in Example 1 was carried out using a non-silane-modified propylene polymer (propylene homopolymer, density: 0.91, MFR: 10), except that thermal degradation was performed at 355°C for 2 hours. went. The obtained low molecular weight propylene polymer had a number average molecular weight of 3,500, a melt viscosity of 165 cps at 160°C, a softening point of 148°C, and a density of 5.0 cps per 1000 carbons.
It was a hard white wax with two double bonds.

Comparative Example 2 The same operation as in Example 1 was carried out using a non-silane-modified propylene polymer (propylene homopolymer, density: 0.91, MFR: 10), except that thermal degradation was performed at 360°C for 2 hours. went. The obtained low molecular weight propylene polymer had a number average molecular weight of 212,900, a melt viscosity at 160°C of 65 cps, a softening point of 145°C, and a molecular weight of 6.5 cps per 1000 carbons.
It was a hard white wax with 0 double bonds.

Comparative Example 3 Using a non-silane modified ethylene polymer (ethylene homopolymer, density: 0.92, MFR: 8),
The same operation as in the example was carried out except that thermal degradation was carried out at 375°C for 2 hours. The obtained low molecular weight ethylene polymer had a number average molecular ffi of 1,900 and a melt viscosity of 28 at 140°C.
0 cps, softening point 107°C, 4.3 per 1000 carbon
It was a hard white wax with double bonds.

Test Example 1 The low molecular weight olefin polymers obtained in Examples 1 to 4 and Comparative Example 3 were evaluated as lubricants for vinyl chloride resins as follows. In the following evaluation, the gelation time represents the time required for the resin to melt uniformly, and it is considered that the longer the gelation time, the greater the lubricity effect.

(1) Plast main test The following vinyl chloride resin composition was kneaded using Labo Plast Kuru (manufactured by Toyo Seiki Seisakusho), and the gelation time was measured. Show the results to the table worker.

[Vinyl chloride resin blend composition] Vinyl chloride resin (Kanevinyl 51001; manufactured by Kanebuchi Chemical Co., Ltd.): 10
0 parts by weight Calcium stearate: 2.5 Zinc stearate = 1.0 Octyl tin malate polymer = o. 5 Lubricant
: 0.5 [Plastomill kneading conditions Temperature: 180"C Rotor rotation speed: 50 rpm Mixing head volume: 80 ml Input sample amount: 72 g Preheating time = 3 minutes (2) Roll test Two rolls of vinyl chloride resin compound as shown below The mixture was kneaded with a roll (manufactured by Eto Seisakusho) and the gelation time and peelability from the roll were measured.The results are shown in Table 1.

[Vinyl chloride resin blend composition] Vinyl chloride resin (Kanevinyl SIOOI): 100
Part by weight dioctyltin mercaptoacetate: 2. O lubricant: 0.5 [Two-roll cross-wire condition Roll temperature: Front roll 175°C, rear roll 180°C Roll rotation speed: 11 x 13 rpm Roll size: 5 inches x 12 inches Cross-wire time: 5 minutes after gelation [Peelability evaluation Standard A: Interfering objects are easily peeled off from the roll surface.

B: The interfering material is difficult to peel off from the roll surface.

(3) Plate-out test After the vinyl chloride resin kneaded material obtained in the above roll test was shaped into a sheet with a thickness of 1 mm using a pressure press, the surface appearance of the pressure plate (roll plated plate) was observed. The results are shown in Table 1.

[Pressure press conditions] Temperature: 180°C Pressure: 100 kg/cm2 Kneaded material: 50 g [Plate out test evaluation criteria] A: Almost no white matter adhered to the pressure plate surface B: Almost all of the pressure plate surface Items (1), (2), and (3) in the table to which white matter adheres correspond to those described in Test Example 1.

[Effects of the Invention] The silane-modified low molecular weight olefin polymer obtained by the present invention has the following effects.

(1) When added as a resin additive, especially to polar resins, it has high lubricity and almost no plate-out phenomenon.

(2) When added to a polar resin, the compatibility is relatively good.

(3) When added to various resins, it has an excellent effect of improving fluidity when molding the resin.

(4) Excellent dispersion effect when mixing pigments, fillers, etc. with various resins.

(5) When added to various resins, it has an excellent effect of improving the water repellency of the surface of the wooden mold.

Since the silane-modified low-molecular-weight olefin polymer obtained by the present invention exhibits the above effects, it is suitable for use as additives for resins, such as lubricants, shaping processability improvers, dispersants for pigments and fillers, and surface modifiers. can.

Claims (1)

[Claims] 1. Polyolefin graft-modified with 0.1 to 10% by weight of a silane compound and having a melt flow rate of 0.1 to 200 in an inert gas at 300 to 450°C.
A method for producing a silane-modified low-molecular-weight olefin polymer having a number average molecular weight of 500 to 20,000, characterized by thermal degradation for 5 to 10 hours. 2. The production method according to claim 1, wherein the number of double bonds in the silane-modified low molecular weight olefin polymer is 1 to 10 per 1000 carbons.